Silicate-based thickener composition

Abstract

The present invention relates to a composition comprising a) a silicate and b) a compound B) having a molecular weight of at least 200 g / mol and comprising at least two groups selected from salts of secondary amines, tertiary amines, or quaternary ammonium amines, and wherein compound B) comprises at least one ester group.

Description

[0001] This invention relates to compositions comprising silicates and amine compounds, to aqueous liquid compositions comprising said compositions, to methods of coating substrates, and to the use of amine compounds to improve the thickening effect of silicates in aqueous compositions.

[0002] In fields such as water-based coatings, adhesives, sealants, molding compounds, water-based drilling fluids, formulations used in construction, formulations for home care, cleaning agents, and personal care, the rheological properties of these liquid systems must be customized—primarily through viscosity adjustment. This can be achieved through the selection of binders, (co)solvents, and the concentration of pigments and / or fillers. Typically, so-called rheology modifiers are added to these liquids. These modifiers work by adjusting the rheological properties of the system, such as viscosity and viscoelastic properties. This typically improves the system's properties in terms of sag resistance, improved storage stability (due to reduced solid particle settling), or a general increase in viscosity (often referred to as "thickening").

[0003] Silicate materials are known to be used as rheology control agents in aqueous liquid compositions. The thickening effect of such rheology control agents can be enhanced by low molecular weight polyamines. WO 91 / 07468 describes the use of polyalkylene polyamines to increase the viscosity of aqueous clay slurries. Examples of suitable amines include ethylenediamine, diethylenetriamine, piperazine, propylenediamine, etc. However, these amines are considered problematic due to occupational safety and industrial hygiene concerns.

[0004] US 5972263 describes treating clay compositions with polyethyleneamine and polyethyleneimine to improve the plasticity of the clay composition. Using such compounds can improve the rheological properties of clay. However, such compounds cause incompatibility in many waterborne coating compositions. This makes them less suitable for improving the thickening effect of silicates in waterborne compositions.

[0005] There is a need for silicate compositions that have improved rheological properties and do not have or mitigate the aforementioned disadvantages.

[0006] This invention provides a composition comprising

[0007] a) Silicates, and

[0008] b) Compound B) having a molecular weight of at least 200 g / mol and comprising at least two groups selected from secondary amines, tertiary amines, salts of secondary or tertiary amines and quaternary ammonium groups, wherein compound B) comprises at least one ester group.

[0009] The compositions of this invention provide improved rheological properties, particularly in aqueous liquid compositions. The compositions exhibit good compatibility with most waterborne coating compositions and possess acceptable properties in terms of occupational safety and industrial hygiene. Compared to compounds B), this composition allows for the use of lower amounts of silica to achieve the desired thickening effect. Alternatively, significantly improved rheological properties can be achieved while maintaining the same amount of silica.

[0010] As mentioned above, the composition contains silicates. Typically, the silicates contain at least one of synthetic clay, natural clay, and silica.

[0011] Suitable synthetic or natural clays include kaolins, smectites, illite, chlorites, or other 2:1 clay types. Specifically, the clay is selected from montmorillonite, bentonite, beidellite, mica, hectorite, saponite, nontronite, sauconite, vermiculite, ledikite, magatite, kenyaite, stevensite, volkonskoite, hydrotalcite, illite, kaolinite, wollastonite, attapulgite, sepiolite, and halloysite. In some embodiments, smectite is preferred. Suitable synthetic or natural clays can be purchased from BYK, for example, by product name. or

[0012] Suitable types of silica include colloidal silica, precipitated silica, and fumed silica. In a preferred embodiment, the silica comprises fumed silica. Fumed silica is also known as pyrolytic silica. Fumed silica is available from various manufacturers, such as Evonik under the trade name Aerosil, Cabot Corporation under the trade name Cab-O-Sil, and Wacker, Dow Corning, Heraeus, and Tokuyama Corporation.

[0013] Generally, it is preferred that the silicates mentioned above exist as inorganic or essentially inorganic materials that have not been modified by treatment with organic compounds, such as hydrophobic agents or organic ion exchangers such as quaternary ammonium compounds.

[0014] The composition further comprises compound B), having a molecular weight of at least 200 g / mol and containing at least two groups selected from secondary amines, tertiary amines, salts of secondary amines or tertiary amines and quaternary ammonium groups, wherein compound B) comprises at least one ester group.

[0015] Compound B and the silicate are not connected by covalent bonds.

[0016] Typically, the molecular weight of compound B) is in the range of 200 g / mol to 4000 g / mol. Preferably, the molecular weight of compound B) is at least 300 g / mol. In a preferred embodiment, the molecular weight of compound B) is in the range of 300 g / mol to 3000 g / mol, or in the range of 350 g / mol to 3000 g / mol. The molecular weight can be suitably determined by gel permeation chromatography. If compound B) has a molecular weight distribution, the molecular weight referred to is the number-average molecular weight Mn determined by gel permeation chromatography using THF (containing 1 vol% dibutylamine) as eluent and calibrated with a polystyrene standard. In some embodiments, compound B) preferably has a molecular weight distribution, i.e., Mw / Mn is greater than 1.00.

[0017] Compound B) preferably has a low content of olefinic unsaturated groups. Therefore, in some embodiments, compound B) contains no or substantially no olefinic unsaturated groups. Typically, compound B) contains 0.0 mmol / g to 2.0 mmol / g, preferably 0.0 mmol / g to 0.1 mmol / g, of olefinic unsaturated groups. The presence of higher amounts of olefinic unsaturated groups in compound B) may impair the stability of the composition and compromise its compatibility with the curing reaction in coating compositions.

[0018] Compound B) contains at least two groups selected from the salts of secondary amines, tertiary amines, secondary amines or tertiary amines and quaternary ammonium groups.

[0019] In a preferred embodiment, compound B) contains at least two groups selected from secondary and tertiary amines or their salts, and is substantially free of or contains no quaternary ammonium groups.

[0020] In a preferred embodiment, compound B) comprises at least one secondary amine group and at least one tertiary amine group.

[0021] In some embodiments, compound B) comprises at least one secondary or tertiary amine group and at least one other group selected from primary, secondary, and tertiary amines. In further embodiments, compound B) comprises at least one secondary or tertiary amine group and further comprises at least one tertiary amine group. In further embodiments, compound B) further comprises at least one hydroxyl group.

[0022] In embodiments of compound B that contain a secondary amine group and a tertiary amine group, it is preferred that the two amino nitrogen atoms are covalently linked to each other via an organic group having 2 or 3 carbon atoms. Highly preferred is that the groups are covalently linked to each other via ethylene or propylene groups.

[0023] In a preferred embodiment, compound B) comprises two tertiary amine groups.

[0024] In a further preferred embodiment, compound B) comprises two secondary amine groups and two tertiary amine groups.

[0025] In a further preferred embodiment, compound B) comprises two secondary amine groups and more than two tertiary amine groups. In another preferred embodiment, compound B) comprises two secondary amine groups and at least four tertiary amine groups.

[0026] Compound B) comprises at least one ester group. In a preferred embodiment, compound B) comprises at least two ester groups. In other embodiments, compound B) comprises three or four ester groups. In a typical embodiment, the number of ester groups is equal to the number of secondary amine groups in compound B). In a preferred embodiment, the number of ester groups is greater than the number of secondary amine groups.

[0027] In some embodiments, compound B) is represented by formula (I).

[0028] R 1 -(-O-(C=O)-CR 2 R 3 -CR 4 R 5 -NR 6 R 7 (I)

[0029] Where R 1 This refers to an organic group having 2 to 300 carbon atoms, preferably 4 to 200 carbon atoms, more preferably 6 to 150 carbon atoms, such as 10 to 100 carbon atoms.

[0030] R 2 R 3 R 4 and R 5 Each can independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, provided that R 2 R3 R 4 and R 5 At least one of them is hydrogen.

[0031] R 6 and R 7 Each can independently represent either hydrogen or an organic group, where R 6 and R 7 At least one of them is not hydrogen, and R is among them. 1 R 6 and R 7 At least one of them contains at least one salt selected from secondary amines, tertiary amines, secondary amines or tertiary amines and a quaternary ammonium group.

[0032] In a preferred embodiment, R 2 R 3 R 4 and R 5 At least two of them represent hydrogen. In a more preferred embodiment, R 2 R 3 R 4 and R 5 At least three of them represent hydrogen. In a highly preferred embodiment, R 2 R 3 R 4 and R 5 Both represent hydrogen.

[0033] In a preferred embodiment, R 6 and R 7 At least one of them represents an organic group containing at least one amine or one hydroxyl group. In a more preferred embodiment, R 6 and R 7 At least one of them represents an aliphatic organic group containing at least one amine or one hydroxyl group. In one embodiment, R 6 and R 7 At least one of them represents an organic group containing at least one amine or one hydroxyl group and at least one ester group.

[0034] In a preferred embodiment, R 7 Represents hydrogen or an organic group containing at least two ester groups, while R 6 Represents an organic group containing 4 to 20 carbon atoms and without an ester group. In a more preferred embodiment, R 7 Represents hydrogen or an organic group containing at least two ester groups, while R 6 Represents an organic group composed solely of atoms selected from carbon, hydrogen, oxygen, and nitrogen, and very preferably, solely of atoms selected from carbon, hydrogen, and nitrogen. In a more preferred embodiment, R 7 Represents hydrogen or an organic group containing at least two ester groups, while R6 It represents an aliphatic organic group containing 4 to 12 carbon atoms, such as 4 to 10 carbon atoms or 5 to 8 carbon atoms.

[0035] In the preferred embodiment, R 1 Contains hydrocarbon groups and other groups of formula (II)

[0036] -(-O-(C=O)-CR 2 R 3 -CR 4 R 5 -NR 6 R 7 (II)

[0037] Where R 2 R 3 R 4 R 5 R 6 and R 7 As defined above.

[0038] Typically, the amine value of compound B) is in the range of 50 to 700 mg KOH / g. Preferably, the amine value of compound B) is in the range of 70 to 650 mg KOH / g, more preferably in the range of 100 to 600 mg KOH / g, and most preferably in the range of 150 to 550 mg KOH / g. The amine value is the amount of KOH in milligrams corresponding to the amine content of 1 gram of substance. The amine value can be determined according to DIN 16945 by potentiometric titration with 0.1N perchloric acid in acetic acid. The amine value can be calculated based on the raw materials used or determined by titration.

[0039] Compound B) above can be prepared by an addition reaction of a compound containing a primary or secondary amine group with a compound having at least one Michael acceptor group. The Michael acceptor group is an electron-depleted alkene unsaturated group that readily accepts nucleophiles. A suitable example of a Michael acceptor group is the double bond of an α,β-unsaturated carboxylic acid ester.

[0040] In a preferred embodiment, compound B) can be prepared by reacting a compound having at least two acrylate functional groups with a compound having a primary or secondary amine group, wherein the primary or secondary amine is used to ensure that substantially all acrylate groups are reacted in molar amounts. Typically, when 1.00 moles of acrylate groups react with a primary amine, about 0.40 to 1.10 moles of a primary amine, preferably 0.75 to 1.05 moles, are used. When 1.00 moles of acrylate groups react with a secondary amine, about 0.90 to 1.10 moles of a secondary amine, preferably 0.95 to 1.05 moles, are used.

[0041] Instead of compounds having at least two acrylate functional groups, compounds having at least two functional groups selected from maleate, fumarate, and itaconic acid groups may also be used, such as unsaturated polyesters based on maleic anhydride (or maleic acid), fumarate, itaconic acid, and mixtures thereof. In another embodiment, compounds having at least one acrylate group and at least one functional group selected from maleate, fumarate, and itaconic acid groups may also be used.

[0042] Examples of suitable starting materials for preparing additives are diacrylates of diols. Preferred diacrylates are C2 to C4. 24 Hydroxyl diols, preferably C3 to C4 18 Hydroxyl diols, more preferably C4 to C5 12 Hydroxyl diols, such as diacrylates of C5 to C8 alkyl diols. Preferably, the alkyl diol is an alkylene diol. These diols can be straight-chain or branched. Suitable diols are simple aliphatic diols, such as 1,6-hexanediol or neopentyl glycol.

[0043] Further preferred diacrylates are diacrylates derived from diols of oligomeric or polyepoxides, such as polyethylene glycol, polypropylene glycol, polybutane glycol, poly(THF), or copolymers of ethylene oxide and / or propylene oxide and / or butane oxide.

[0044] Diacrylates of diols based on hydrocarbon diols, preferably alkylene diols, are particularly preferred.

[0045] Acrylates of alcohols having more than two hydroxyl groups are also suitable, such as trimethylolpropane, glycerol, pentaerythritol, bis(trimethylolpropane) or dipentaerythritol, and their alkoxylated derivatives.

[0046] Further examples include polyester difunctional, trifunctional, or polyfunctional acrylates based on a polyester backbone terminated with acrylate groups. Alternatively, so-called epoxy acrylates may be used, which can be prepared by adding acrylic acid to an epoxy-functionalized precursor. Examples of suitable epoxy-functionalized precursors are copolymers of epoxidized natural oils, aromatic or aliphatic glycidyl ethers, and epoxy-functionalized polymers, such as copolymers of glycidyl methacrylate obtained by polymerization of their double bonds.

[0047] It is also possible to use urethane acrylates, which can be prepared by reacting hydroxy-functional acrylates with aliphatic or aromatic isocyanates having two or more isocyanate groups.

[0048] The primary or secondary amines that can be added to the Michael acceptor group in the above reaction are typically primary or secondary amines with a molecular weight in the range of 31 to about 1200 g / mol, more preferably 45 to about 500 g / mol, and even more preferably 59 to about 300 g / mol. Aliphatic amines and aryliphatic amines are preferred.

[0049] In some embodiments, the primary or secondary amine has an additional functional group. Examples of suitable additional functional groups are hydroxyl, tertiary amine, ammonium, and thiol groups. So far, very good results have been obtained in embodiments where the additional functional group is a tertiary amine or hydroxyl group. Examples of suitable amine starting materials include primary and secondary aliphatic or aryliphatic monoamines and diamines. Very good results have been obtained with aliphatic primary and secondary amines having an additional tertiary amine group or an additional hydroxyl group.

[0050] Therefore, preferred amine starting materials are aminoethanol, 1-aminoprop-2-ol, 1-aminoprop-3-ol, aminobutanol, aminopentanol, aminohexanol, 2-amino-2-(hydroxymethyl)prop-1,3-diol, dihydroxydiethylamine, 2-ethyl-2-aminopropanediol, D-glucosamine, N-methyl-D-glucosamine, 1-(3-aminopropyl)imidazolium, N,N-dimethyl-1,3-diaminopropane, 3-(methylamino)propylamine, N,N,N”,N”-tetramethyldipropylenetriamine, N,N-diethylethylenediamine, and 1-methylpiperazine.

[0051] In some embodiments, compound B) is prepared by an addition reaction of a primary or secondary amine having an additional functional group, said additional functional group being a primary or secondary amine group. If a molecule having one or more primary amine groups is used in such a reaction, it is sometimes preferred to use a molar excess of the primary amine group relative to the Michael acceptor group.

[0052] Preferred amine starting materials are diamines, such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane.

[0053] The preferred amine starting material is an amine having more than two primary amine groups, namely 2,2',2”-triaminotriethylamine.

[0054] Preferred amine starting materials having two or more amino groups (at least one of which is a secondary amino group) are triazacyclononane, piperazine, 2-methylpiperazine, N,N'-diethylethylenediamine, N,N-dimethylaminoethyl-piperazine, 3-(methylamino)propylamine, bis-(2-aminoethyl)amine, triethylenetetramine, and tetraethylenepentamine.

[0055] In some embodiments, compound B) comprises an amine salt or a quaternary ammonium group. As known to those skilled in the art, amine salts can be obtained by partially or completely neutralizing the amine with a Brønsted acid; such acid can be an organic or inorganic acid. Quaternary ammonium groups can be obtained by treating a tertiary amine with an alkylating agent.

[0056] The addition of a primary amine group to a Michael acceptor group (such as an acrylate group) yields a secondary amine group. This secondary amine group can then further add to the same or different Michael acceptor groups. If this occurs, the molecular weight of the reaction product increases, and the molecular weight distribution typically broadens.

[0057] In a typical implementation, compound B) is represented by formula (III).

[0058]

[0059] Where at least 50 to 100 mol% of group A represents a group of the following formula.

[0060] -(-O-(C=O)-CR 2 R 3 -CR 4 R 5 -NR 6 R 7 (II)

[0061] Where R 1 R 2 R 3 R 4 R 5 R 6 and R 7 As defined above, and

[0062] n is an integer in the range of 1 to 15, preferably 1 to 10, such as 1 to 7.

[0063] If a particular group appears more than once in a given molecule, they can be chosen independently of each other each time they appear.

[0064] In a preferred embodiment, the group R of formula (III) 1 This represents a hydrocarbon group containing 2 to 24 carbon atoms, preferably 3 to 18 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 8 carbon atoms. Preferably, R... 1 It can be a saturated or unsaturated, straight-chain or branched aliphatic group. Preferably, R 1 It is a saturated group. In one embodiment, R 1 Represents an alkylene group.

[0065] In a preferred embodiment, at least 70 mol% of group A, more preferably at least 85 mol% of group (II), represents the group of formula (II).

[0066] When less than 100 mol% of group A is a group of formula (II), the remaining group A represents an olefinically unsaturated polymerizable group, preferably an acrylate or methacrylate group.

[0067] In the compositions of the present invention, the weight ratio of silicate and compound B) can vary over a wide range. However, the amount of compound B) generally does not exceed the amount of silicate. In a preferred embodiment, compound B) is present in an amount of 3.0 to 100.0% by weight, preferably 5.0 to 60.0% by weight, based on the weight of silicate. In the most preferred embodiment, compound B) is present in an amount of 7.0 to 50.0% by weight, such as 8.0 to 40.0% by weight, based on the weight of silicate.

[0068] The compositions of the present invention are well-suited as rheology control additives for liquid compositions, preferably aqueous liquid compositions. Therefore, the present invention also relates to aqueous liquid compositions comprising the compositions according to the present invention as described above.

[0069] The term "liquid composition" refers to a composition that is liquid at 23°C and 100 kPa, i.e., involves at least two substances. In this invention, the term "liquid" refers to any liquid medium, regardless of its viscosity. Liquids therefore include both very low viscosity media and high viscosity media, such as pastes.

[0070] A liquid composition is defined as an aqueous composition when at least 50% by weight of all volatile liquids in the composition are water. Preferably, 50 to 100% by weight of all volatile liquids in the composition are water, more preferably 70 to 100% by weight of all volatile liquids in the composition, such as 80 to 100%, 90 to 100%, or 95 to 100% by weight of all volatile liquids in the composition. A volatile liquid is defined as a liquid with a boiling point below 250°C at 100 kPa.

[0071] Examples of suitable aqueous liquid compositions include: coating compositions, plastic formulations, pigment pastes, polymer formulations, sealant formulations, cosmetic formulations, household or industrial care formulations (including fragrance and perfume formulations), ceramic formulations, flooring formulations, adhesive formulations, liquid formulations for oil and gas extraction, compositions for the manufacture of electrical components and circuits, liquid formulations for energy storage media, cleaning agents, potting compounds, building material formulations, lubricants, filler compounds, wax emulsions, metalworking fluids, metalworking products, liquid compositions in the form of sprays, so-called deposition aids (e.g., for plant protection agents or for general purposes of reducing drift), inks, and mixtures thereof.

[0072] Other aqueous liquid compositions that can be used with the compositions according to the invention include aqueous paints (such as marine and protective coatings, automotive coatings, general industrial coatings, can and roll coatings, decorative paints and wall paints), printing inks, and inks and lacquers, such as lacquers for varnishing plastics, wire enamels, floor coatings, coating compositions for coating food and seeds, and so-called color resists (used, for example, in color filters in flat panel displays, such as liquid crystal displays). Applications of paints also include paste-like materials that typically have a very high solids content and a low liquid component content, such as so-called pigment pastes or pastes based on effect pigments, such as metallic effect pigments, such as aluminum pigments, silver pigments, brass pigments, zinc pigments, copper pigments, bronze pigments such as gold bronzes, fire-dyed bronzes, or iron oxide aluminum pigments. Effect pigments also include, for example, interference pigments or pearlescent pigments, such as metal oxide mica pigments, fishsilver, bismuth oxychloride, or basic lead carbonate.

[0073] Cosmetic products can be various liquid compositions used in the so-called personal care or health care industry, such as lotions, creams, pastes (e.g., toothpaste), foams (e.g., shaving foam), gels (e.g., shaving gel, shower gel, or active ingredients in gel formulations), shampoos, liquid soaps, nail varnishes, lipsticks, and hair dyes. So-called wax emulsions are preferably dispersions of solid waxes in particulate form at room temperature in an aqueous medium. Building material formulations can be liquid or paste-like materials used in the construction industry and solidifying upon curing, such as concrete, mortar, putty, plaster, tile adhesives, cementitious materials, and gypsum-based materials. Metalworking fluids can be cutting fluids, drilling fluids (e.g., forging fluids), or generally, lubricants. Other possible areas include mold release agents (e.g., for aluminum die casting and casting applications), foundry washes, and liquids used for surface treatment of metals. Lubricants are used for lubrication, that is, to reduce friction and wear, as well as to provide power, cooling, vibration damping, sealing, and corrosion protection. Cleaning agents are used to clean a wide variety of objects, for example in household or industrial care. They achieve or assist in the removal of impurities, residues, and deposits. Cleaning agents also include detergents (primarily used for cleaning textiles, their precursors, leather, and tableware) and personal care products. Formulations containing fragrances and other flavorings (as liquid raw materials or in encapsulated form), such as perfume gels, also fall into this application area.

[0074] Adhesives can be any adhesive material that is liquid under processing conditions and can bond components through surface adhesion and internal strength. Sealants (including caulking agents) can be any material that is liquid under processing conditions and can act as a mechanical seal, preferably used to block the passage of fluids, gases, or particles (e.g., dust) through surfaces, joints, or openings in materials, as well as the transmission of sound and / or temperature.

[0075] Liquid formulations used in oil and gas extraction are those used to open and exploit reservoirs. Drilling fluids or "drilling mud" are a preferred example. Another application example is fluids used to prepare for or perform hydraulic fracturing.

[0076] The aqueous liquid compositions of the present invention may further comprise conventional additives. Examples of additives include anti-blocking agents, stabilizers, antioxidants, pigments, wetting agents, dispersants, emulsifiers, additional rheology modifiers, UV absorbers, free radical scavengers, slip additives, defoamers, adhesion promoters, leveling agents, waxes, nanoparticles, film-forming aids, and flame retardants. Preferred additives are wetting agents, dispersants, and / or emulsifiers, and rheology modifiers different from those in the compositions of the present invention.

[0077] Preferably, the aqueous liquid composition is substantially free of volatile organic solvents. This means a composition suitably comprising 0.0 to less than 15.0%, preferably less than 10.0% by weight, of volatile organic solvents based on the total weight of the non-aqueous liquid composition, more preferably 0.0 to 7.0% by weight. More preferably, the aqueous liquid composition comprises less than 5.0% by weight of volatile organic solvents.

[0078] The aqueous liquid composition may suitably further comprise a film-forming binder. The film-forming binder is different from compound B. The film-forming binder can be dissolved in the aqueous phase of the aqueous liquid composition. In an alternative embodiment, the film-forming binder is present in the aqueous phase in the form of dispersed droplets or particles.

[0079] The film-forming adhesive can be any of those known to be suitable for aqueous compositions.

[0080] In a typical implementation, the film-forming binder comprises at least one of polyacrylate, styrene copolymer, polyethylene ester, polyurethane, polyester, polyunsaturated resin, and epoxy resin.

[0081] Polyacrylates are polymers and copolymers of esters or amides of acrylic acid and methacrylic acid, optionally combined with other olefinically unsaturated polymerizable monomers. Polyvinyl esters are polymers and copolymers of vinyl esters such as vinyl acetate or vinyl butyrate, and copolymers with other unsaturated monomers.

[0082] In a preferred embodiment, the aqueous liquid composition comprises 0.10 to 7.00% by weight of silicate, calculated based on the weight of the aqueous liquid composition.

[0083] The aqueous liquid composition suitably contains

[0084] i) 0.10 to 37.00% by weight of silicates

[0085] ii) 0.01 to 37.00% by weight of compound B)

[0086] iii) 25.00 to 99.89% by weight of film-forming binder,

[0087] Calculated based on the total weight of components i), ii), and iii). Film-forming binder iii) comprises the resin used, as well as all components capable of forming covalent bonds with the resin, such as hardeners and reactive diluents.

[0088] Preferably, the aqueous liquid composition contains

[0089] i) 0.20 to 31.00% by weight of silicates

[0090] ii) 0.02 to 31.00% by weight of compound B)

[0091] iii) 38.00 to 99.78% by weight of film-forming adhesives,

[0092] Calculated based on the total weight of components i), ii), and iii).

[0093] More preferably, the aqueous liquid composition comprises

[0094] i) 0.30 to 29.00% by weight of silicates

[0095] ii) 0.03 to 29.00% by weight of compound B)

[0096] iii) 42.00 to 99.67% by weight of film-forming binder,

[0097] Calculated based on the total weight of components i), ii), and iii).

[0098] In one embodiment, the above-described aqueous liquid composition is formulated as a coating composition. Therefore, the present invention further relates to a method of coating a substrate with at least one coating, comprising applying the coating composition to the substrate.

[0099] As mentioned above, compound B) improves the rheological properties of silicates in aqueous compositions. Therefore, the present invention further relates to the use of compound B) for improving the rheological properties of silicates in aqueous compositions, said compound B) having a molecular weight of at least 200 g / mol and comprising at least two groups selected from secondary amines, tertiary amines, salts of secondary or tertiary amines and quaternary ammonium groups, and wherein compound B) comprises at least one ester group.

[0100] The present invention further relates to a method for improving the rheological properties of silicates in aqueous compositions, comprising including a compound B) in the composition, said compound B) having a molecular weight of at least 200 g / mol and comprising at least two groups selected from salts of secondary amines, tertiary amines, or quaternary ammonium amines, and wherein compound B) comprises at least one ester group.

[0101] Rheological effect refers to the alteration of viscosity or viscoelastic properties according to the intended use. Typically, compositions of silicates and compound B are used to increase the viscosity of aqueous liquid compositions, resulting in a thickening effect and improved anti-sagging behavior.

[0102] Silicates are typically solids. Compound B) can be a solid or a liquid. Compound B) can be liquid itself or dissolved in a suitable organic solvent. The solvent can be any kind of organic solvent capable of dissolving compound B). Preferably, the solvent is soluble or dispersible in water; further preferably, the solvent is non-toxic and has eco-friendly characteristics. In a preferred embodiment, the solvent is a non-volatile liquid with a boiling point of 250°C or higher at atmospheric pressure. Particularly preferred solvents are polymers and oligomers of epoxides such as ethylene oxide and / or propylene oxide. These can be homopolymers, such as polyethylene glycol or polypropylene glycol, but can also be random and block copolymers. In some embodiments, the polymers or oligomers of ethylene oxide and / or propylene oxide have one or two ether end groups, particularly alkyl ether end groups, wherein the alkyl group has 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms. In other embodiments, the polymers or oligomers of ethylene oxide and / or propylene oxide have two hydroxyl end groups. These oligomerizing or polymerizing solvents typically have a number average molecular weight in the range of 170 to 1000 g / mol, preferably 200 to 800 g / mol.

[0103] The silicate and compound B) can be suitably added simultaneously or sequentially to the aqueous liquid composition. In a preferred embodiment, the silicate and compound B) are mixed before they are added to the aqueous liquid composition. The mixing process can be provided by any mixing equipment known in the art, such as various mills or extruders. In a different embodiment, compound B) can be premixed with an adsorbent different from the silicate before being mixed with it. In a further embodiment, compound B) can be provided in a sealed package. Example

[0104] Preparation of compound B)

[0105] Example 1

[0106] 45.26 g (0.200 mol) of 1,6-hexanediol diacrylate (HDDA) and 86.10 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0107] 40.84 g (0.400 mol) of N,N-dimethylaminopropylamine (DMAPA) was added over 20 minutes using a dropping funnel. The reaction was slightly exothermic and the temperature did not exceed 50°C. The mixture was stirred at 50°C for 3 hours. The resulting product was a viscous orange liquid.

[0108] Examples 2 and 3 were prepared similarly, but using different molar ratios summarized in Table 1 below.

[0109] Table 1

[0110] 1 45.26 0.200 40.84 0.400 1 / 2 Liquid, orange, clear 2 45.26 0.200 30.63 0.300 2 / 3 Liquid, yellow, clear 3 67.89 0.300 40.84 0.400 3 / 4 Liquid, yellow, clear

[0111] Example 4

[0112] 24.23 g (0.100 mol) of dipropylene glycol diacrylate and 44.65 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0113] 20.42 g (0.200 mol) of N,N-dimethylaminopropylamine was added over 20 minutes using a dropping funnel. The reaction was slightly exothermic and the temperature did not exceed 50°C. The mixture was stirred at 50°C for 3 hours. The resulting product was a viscous yellow liquid.

[0114] Example 5

[0115] 30.04 g (0.100 mol) of tripropylene glycol diacrylate and 50.46 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0116] 20.42 g (0.200 mol) of N,N-dimethylaminopropylamine was added over 20 minutes using a dropping funnel. The reaction was slightly exothermic and the temperature did not exceed 50°C. The mixture was stirred at 50°C for 3 hours. The resulting product was a viscous yellow liquid.

[0117] Example 6

[0118] 24.23 g (0.050 mol) of bisphenol A glycerolate diacrylate and 34.44 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0119] 10.21 g (0.100 mol) of N,N-dimethylaminopropylamine was added over 20 minutes using a dropping funnel. The reaction was slightly exothermic and the temperature did not exceed 50°C. The mixture was stirred at 50°C for 3 hours. The resulting product was a viscous yellow liquid.

[0120] Example 7

[0121] 44.00 g (0.222 mol) of butanediol diacrylate and 84.84 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0122] 40.84 g (0.400 mol) of N,N-dimethylaminopropylamine was added over 20 minutes using a dropping funnel. The reaction was slightly exothermic and the temperature did not exceed 50°C. The mixture was stirred at 50°C for 3 hours. The resulting product was a viscous, turbid liquid.

[0123] Example 8

[0124] 21.22 g (0.100 mol) of neopentyl glycol diacrylate and 41.66 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0125] 20.42 g (0.200 mol) of N,N-dimethylaminopropylamine was added over 20 minutes using a dropping funnel. The reaction was slightly exothermic and the temperature did not exceed 50°C. The mixture was stirred at 50°C for 3 hours. The resulting product was a viscous, slightly turbid, colorless liquid.

[0126] Example 9

[0127] 22.63 g (0.100 mol) of 1,6-hexanediol diacrylate and 45.87 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0128] 23.24 g (0.200 mol) of N,N-diethylethylenediamine was added over 20 minutes using a dropping funnel. The reaction was slightly exothermic and the temperature did not exceed 50°C. The mixture was stirred at 50°C for 3 hours. The resulting product was a viscous, slightly turbid, colorless liquid.

[0129] Example 10

[0130] 22.63 g (0.100 mol) of 1,6-hexanediol diacrylate and 60.09 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0131] 37.46 g (0.200 mol) of 3,3′-iminobis(N,N-dimethylpropylamine) was added over 20 minutes using a dropping funnel. The reaction was slightly exothermic and the temperature did not exceed 50°C. The mixture was stirred at 50°C for 3 hours. The resulting product was a viscous, slightly turbid, colorless liquid.

[0132] Example 11

[0133] 48.60 g (0.15 mol) of polyethylene glycol-200 diacrylate and 76.95 g of methoxy (polyethylene glycol)-350 were loaded into a four-necked round-bottom flask equipped with a stirrer, thermometer and reflux condenser and heated to 30 °C under a nitrogen atmosphere.

[0134] 31.54 g (0.30 mol) of diethanolamine was added over 20 minutes using a dropping funnel. The mixture was stirred at 40°C for 3 hours. The resulting product was a turbid liquid.

[0135] Application Examples

[0136] Raw materials:

[0137] Table 2

[0138]

[0139] Experimental system: Styrene-acrylic white paint

[0140] Styrene-acrylic white paint was prepared using the formulations in Table 3. All mill base materials were filled into a double-walled grinding jar and dispersed under the specified conditions. After dispersion, let-down was added under the conditions specified in Table 3. The pH of the control sample and the clay-containing formulation was then adjusted to pH 8.5 using AMP 90. Subsequently, the silicate-containing formulation was aliquoted into 70-gram portions in 100-mL glass vials for preparation. Amine functional compound B and the control compound were added to these portions at 15% by weight, based on the amount of silicate, while stirring for 5 minutes at room temperature (23°C) using a Dispermat LC3 (VMAGetzmann) at 1500 rpm with a 2.5 cm diameter toothed plate.

[0141] After being stored overnight at room temperature, samples were applied with wet film thicknesses of 30-300 or 50-500 μm using a stepped doctor blade (Model 421 / S, Erichsen GmbH & Co KG) for sagging resistance testing. Application was performed on contrast cards (BYK-Gardner GmbH) at an application speed of 50 mm / s using an automated applicator (byko-drive XL, BYK-Gardner GmbH). For this measurement, the stepped doctor blade was used to apply coatings of varying thicknesses. A defined distance was created between two stripes of different thicknesses by the doctor blade. If sagging resistance is unacceptable, this results in a reduced distance between two adjacent coating strips, or worse, strips flowing into each other. Other unacceptable results include the formation of runners and bulges. After application, the drawn-down was hung vertically at room temperature until dry. Sagging resistance was then visually evaluated after drying. Therefore, the highest wet film thickness exhibiting clear separation between two adjacent coating strips after drying, without channel formation or bulge building, was considered. In addition to application, viscosity was measured at 0.4 1 / s using a Physica MCR301 rheometer (Anton Paar GmbH) with the following parameters: CSR measurement, cone 2.5 cm 1°, shear rate approximately 0.1–1000 1 / s, at 23°C. The gloss of the formulation was measured at 60° using an mcro-tri gloss meter (BYK Gardner GmbH) in the second line of a stepped doctor blade application at a wet film thickness of 100 μm, and the seeding tendency was visually assessed in the first line of a stepped doctor blade application at a wet film thickness of 50 μm.

[0142] Table 3: Styrene-acrylic white paint formulations

[0143]

[0144] Dispermat CV, 2 min, 1000 rpm, 4.0 cm diameter toothed plate

[0145] Table 4: Application Results

[0146]

[0147] The comparative examples in Table 4 are marked with *.

[0148] Examples marked with # contain 30% by weight (not 15% by weight) of compound B based on the amount of silicate.

[0149] As can be seen from Table 4, compared with the samples of the present invention containing clay and compound B), the comparative formulation C containing only silicate (Optigel CK) without compound B and the comparative formulation B containing only compound B from Preparation Example 1 without clay exhibited significantly lower anti-sagging properties and viscosity. All compounds B according to the present invention improve the rheological properties of silicates and thus increase their efficiency, without negatively affecting gloss and crystallization tendency.

[0150] Although contrast formulations D and E also improve the rheological properties of silicates, they have a significant negative impact on the gloss and seeding tendency of the varnish. Contrast formulation F shows a smaller negative impact on gloss, but the rheological improvement is not very significant, and although it slightly increases anti-sagging properties, this contrast formulation also has a negative impact on seed formation.

[0151] Experimental system: Unsaturated polyester system

[0152] raw materials

[0153] Table 5

[0154] Palatal P4-01 Unsaturated polyester resin Aliancys AG ECOS ND 15 Cobalt Octoat Umicore AG&Co.KG Aerosil 200 Hydrophilic fumed silica Evonik Operations GmbH

[0155] The unsaturated polyester system was prepared using the formulations in Table 6. All components were added to a PE tank under stirring and homogenized for 15 minutes at room temperature (23°C) using a Dispermat CV (VMA Getzmann), 3100 rpm, 9 cm diameter toothed plate. The system was aliquoted into smaller amounts (100 g in 150 mL glass vials) and incorporated into the embodiments of the invention at a dosage of 20% by weight (based on the weight of Aerosil 200) of Compound B under stirring for 5 minutes at room temperature (23°C) using a Dispermat LC3 (VMA Getzmann), 1000 rpm, 2.5 cm diameter toothed plate. After overnight storage at room temperature, samples were applied to the samples with a wet film thickness of 50-500 μm using a stepped doctor blade (Model 421 / S, Erichsen GmbH & Co KG) for anti-sagging testing. Film application was performed on a contrast card 2801 (BYK-Gardner GmbH) using an automated film applicator, byko-drive XL (BYK-Gardner GmbH), at an application speed of 50 mm / s. After application, the coated material was hung vertically at room temperature until dry. Sagging resistance was visually evaluated after drying. Therefore, the maximum wet film thickness exhibiting clear separation of the coated material after drying, without flow channels, and without bulge building between applied film thicknesses was considered.

[0156] Table 6: Unsaturated Polyester Systems

[0157]

[0158] Table 7: Results

[0159] Controls (without Aerosil and without compound B) <50 Reference (Aerosil 200 only, no compound B) 200 Aerosil 200+ Example 1 300 Aerosil 200+ Example 2 300 Aerosil 200+ Example 3 350 Aerosil 200+ Example 11 300 Aerosil 200+Lupasol WF* 200 Aerosil 200+Epomin-SP 003* 250

[0160] *): As with the embodiments of the present invention, the non-inventory embodiments Lupasol WF and Epomin-SP 003 are also incorporated at a dose of 20% by weight (based on the weight of Aerosil 200).

[0161] Table 7 shows that, compared with the non-invention comparative examples, the rheology additives of the present invention can achieve better anti-sagging properties in unsaturated polyester formulations.

Claims

1. A composition comprising a) Silicates, and b) Compound B), having a molecular weight of at least 200 g / mol and comprising at least two groups selected from secondary amines, tertiary amines, salts of secondary or tertiary amines, and quaternary ammonium groups, wherein compound B) comprises at least one ester group. Compound B and the silicate are not connected by covalent bonds. Compound B is represented by the following formula (I). R 1 -(-O-(C=O)-CR 2 R 3 -CR 4 R 5 -NR 6 R 7 (I) Where R 1 Represents organic groups having 2 to 300 carbon atoms. R 2 R 3 R 4 and R 5 Each can independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, provided that R 2 R 3 R 4 and R 5 At least one of them is hydrogen. R 6 and R 7 Each can independently represent either hydrogen or an organic group, where R 6 and R 7 At least one of them is not hydrogen, and R is among them. 1 R 6 and R 7 At least one of them contains at least one salt selected from secondary amines, tertiary amines, secondary amines or tertiary amines and a quaternary ammonium group.

2. The composition according to claim 1, wherein compound B) comprises an amount of olefinic unsaturated groups from 0.0 mmol / g to 2.0 mmol / g.

3. The composition according to claim 1 or 2, wherein compound B) has a molecular weight in the range of 200 to 4000 g / mol.

4. The composition according to any one of claims 1 to 3, wherein compound B) comprises at least two tertiary amine groups.

5. The composition according to any one of claims 1 to 4, wherein compound B) comprises at least two ester groups.

6. The composition according to any one of claims 1 to 5, wherein the silicate comprises at least one of synthetic clay and natural clay.

7. The composition according to claim 6, wherein the synthetic or natural clay comprises montmorillonite.

8. The composition according to any one of claims 1 to 7, wherein compound B) is present in an amount of 3.0 to 100.0% by weight based on the weight of the silicate.

9. The composition according to claim 8, wherein compound B is present in an amount of 5.0 to 60.0% by weight based on the weight of the silicate.

10. An aqueous liquid composition comprising the composition according to any one of claims 1 to 9.

11. The aqueous liquid composition of claim 10, further comprising a film-forming binder.

12. The aqueous liquid composition of claim 11, wherein the film-forming binder comprises at least one of polyacrylate, styrene copolymer, polyethylene ester, polyurethane, polyester, polyunsaturated resin and epoxy resin.

13. The aqueous liquid composition according to any one of claims 10 to 12, wherein the aqueous liquid composition comprises 0.10 to 7.00% by weight of silicate based on the weight of the aqueous liquid composition.

14. The aqueous liquid composition according to any one of claims 10 to 13, wherein the composition is formulated as a coating composition.

15. A method of coating a substrate with at least one coating, comprising applying the composition according to claim 14 onto the substrate.

16. Use of compound B) for improving the rheological properties of silicates in aqueous compositions, said compound B) having a molecular weight of at least 200 g / mol and comprising at least two groups selected from secondary amines, tertiary amines, salts of secondary or tertiary amines, and quaternary ammonium groups, and wherein compound B) comprises at least one ester group. Compound B and the silicate are not connected by covalent bonds. Compound B is represented by the following formula (I). R 1 -(-O-(C=O)-CR 2 R 3 -CR 4 R 5 -NR 6 R 7 (I) Where R 1 Represents organic groups having 2 to 300 carbon atoms. R 2 R 3 R 4 and R 5 Each can independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, provided that R 2 R 3 R 4 and R 5 At least one of them is hydrogen. R 6 and R 7 Each can independently represent either hydrogen or an organic group, where R 6 and R 7 At least one of them is not hydrogen, and R is among them. 1 R 6 and R 7 At least one of them contains at least one salt selected from secondary amines, tertiary amines, secondary amines or tertiary amines and a quaternary ammonium group.

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