Composition containing an associative thickener

Abstract

This invention provides a high-quality thickening agent composition with good efficacy that improves the color viscosity stability in aqueous application systems. [Solution] A thickening agent composition comprising at least one anionic surfactant and at least one associative thickening agent, wherein the associative thickening agent comprises: - at least one polyether segment and - at least one hydrophobic segment according to formula (I) Includes JPEG2026511111000034.jpg4279, In formula (I), R 4 A thickening agent composition wherein each of the following is independently hydrogen, alkyl, cycloalkyl, aryl, or arylalkyl, and at least one associative thickening agent comprises at least one of HEUR and HEAT thickening agents.

Description

[Technical Field]

[0001] The present invention relates to a thickening agent composition comprising at least one anionic surfactant and at least one associative thickener, wherein the associative thickener comprises at least one polyether segment and at least one hydrophobic segment. The present invention further relates to a liquid composition comprising the thickening agent composition, the use of the composition to improve the color viscosity stability of a colored liquid composition, a method for improving the color viscosity stability of a liquid composition, and a coated article. [Background technology]

[0002] In fields such as coating materials, adhesives, sealants, and molding compounds, as well as oil field drilling fluids, it is necessary to customize the rheological properties of such liquid systems, primarily by adjusting viscosity and flow behavior. This can be done, for example, by selecting the concentrations of binders, solvents, and pigments and / or fillers. Often, the addition of so-called rheological additives to these liquids is required. The effect of these additives is to adjust the rheological properties of the system, such as viscosity and viscoelastic properties. Additives can be used to increase or maintain the viscosity of compositions used in applications including, but not limited to, latex paints, cleaning agents, cosmetics, aqueous pigment pastes, automotive finishes, industrial coatings, printing inks, lubricating greases, textile coatings, pharmaceutical formulations, agricultural formulations, filler dispersions, adhesives, detergents, wax dispersions, drilling fluids, fire extinguishing foams, and / or abrasives. Such additives are generally called "thickeners." Thickeners can improve and / or influence other properties in specific application systems, particularly aqueous systems. For example, associative thickeners used in latex paints can improve and control the viscosity of the paint, protect colloidal action, and improve pigment suspension, leveling, and flow. While associative thickeners for aqueous systems have been used to thicken aqueous compositions, there is a need for improved thickeners for use in aqueous compositions containing large amounts of pigment and / or strongly colored pigments. When associative thickeners are used in aqueous formulations such as paints, undesirable side effects often occur, and the colored viscosity is unstable; that is, the viscosity of the paint changes upon coloring.

[0003] A problem that arises in paints containing associative thickeners is the change in viscosity when the pigment composition is added to the paint formulation (coloring). This often affects the viscosity in the low shear range. Low shear viscosity is when the applicable shear rate is 0.1 s. -1 ~400s -1This is the viscosity exhibited when the paint is within a certain range. Low shear conditions are typically seen in paints that are still in a can and immediately after being applied to a wall. During these stages, a sufficiently low shear viscosity is required to resist pigment settling and film sagging, but to provide the necessary leveling of the applied coating. As the colored paints market continues to grow, all currently available approaches to mitigate viscosity changes have limitations. Therefore, there remains a need to provide compositions that can be used as additives in water-based paints and coating formulations to reduce viscosity changes during coloring.

[0004] For example, combinations of two or more associative thickeners are used in paints to obtain a desired balance of high and low shear viscosity. Common combinations include pseudoplastic associative thickeners for controlling low to medium shear viscosity and relatively Newtonian associative thickeners for controlling high shear viscosity. U.S. Patent Application Publication 2007 / 0155880 discloses the selection of two associative thickeners with higher and lower molecular weights and their use in combination at a specific concentration ratio. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Therefore, there is still a need to provide improved associative thickeners for aqueous systems. The use of thickeners should be highly reliable, resulting in increased thickening effect and high viscosity stability during coloring. Furthermore, they should exhibit a positive effect on the gloss and color stability of the applied system.

[0006] Therefore, an object of the present invention is to provide a high-quality thickening agent composition that has good efficacy in improving color viscosity stability, particularly in aqueous application systems. Another object of the present invention is to provide an associative thickening agent composition that improves gloss and color stability in coated paints. [Means for solving the problem]

[0007] Surprisingly, these objectives can be achieved by a thickening agent composition comprising at least one anionic surfactant and at least one associative thickener, the associative thickener being - At least one polyether segment, and - At least one hydrophobic segment according to formula (I) [ka] Includes, In the formula, R 4 Each of these is independently hydrogen, alkyl, cycloalkyl, aryl, arylalkyl, preferably hydrogen, methyl, butyl, phenyl, or benzyl, and at least one associative thickener comprises at least one of the HEUR and HEAT thickeners. [Modes for carrying out the invention]

[0008] The term "associative thickener" refers to a nonionic, hydrophobically modified, water-soluble polymer that can interact with itself and with other species, such as latex particles, in aqueous solutions.

[0009] Examples of different types of associative thickeners include, but are not limited to, polyurethanes, polyesters, modified celluloses, polyester-urethanes, polyether-alphaolefins, aminoplast-ether copolymers, and polyether-polyols. Preferably, the associative thickener comprises at least one of the aforementioned compounds.

[0010] Associative thickeners generally contain one or more hydrophilic moieties coupled with one or more hydrophobic moieties. In some embodiments of an associative thickener, one or more hydrophilic moieties are linked to one or more hydrophobic moieties via one or more coupling moieties. In some embodiments, the coupling moieties may be difunctional moieties, trifunctional moieties, or moieties with higher functional groups. Difunctional coupling moieties may be coupled to any combination of two moieties selected from the hydrophilic and / or hydrophobic moieties. Trifunctional coupling moieties may be coupled to any combination of three hydrophilic and / or hydrophobic moieties. It should be understood that each hydrophobic moiety and each hydrophilic moiety do not need to be identical. In some embodiments, some or all of the hydrophobic and hydrophilic moieties may be different. In certain embodiments, all of the hydrophobic moieties may be identical, or all of the hydrophilic moieties may be identical. The same applies to the coupling moieties. If multiple coupling moieties exist, those coupling moieties may be identical or different.

[0011] The reactants that form the hydrophilic portion of an associative thickener are generally at least bifunctional in order to allow coupling to at least two different reactants that form the coupling portion. In some embodiments, they are bifunctional. The reactants that form the hydrophilic portion of the associative thickener are polyethers (also known as polyether polyols). The polyether may be an adduct of an aliphatic, alicyclic, or aromatic polyhydroxy compound with an alkylene oxide. Examples of polyhydroxy compounds include, but are not limited to, polyhydric alcohols or polyhydric alcohol ethers.

[0012] Examples of the alkylene oxide compound include, but are not limited to, ethylene oxide and / or propylene oxide. Examples of the polyhydric alcohol include, but are not limited to, glycol, polyalkylene glycol, a hydroxy compound containing three or more hydroxyl groups, or a mixture thereof. Examples of the glycol include, but are not limited to, ethylene glycol and / or propylene glycol. Examples of the hydroxy compound containing three or more hydroxyl groups include, but are not limited to, glycerol, erythritol, sorbitol, mannitol, trimethylolpropane, pentaerythritol, or a mixture thereof. Examples of the polyalkylene glycol include, but are not limited to, polyethylene glycol, polypropylene glycol, polybutylene glycol, or a mixture or copolymer thereof. The polyalkylene glycol may have a number average molecular weight of 2,000 to 35,000 g / mol. Examples of the alicyclic polyhydric alcohol include, but are not limited to, 1,2-cyclopentanediol, 1,4-cyclohexanediol, and / or hexahydroxycyclohexane. Examples of the aromatic polyhydric alcohol include, but are not limited to, dihydroxybenzene and trihydroxybenzene.

[0013] Preferred is polyethylene glycol, and particularly preferred is polyethylene glycol having a number average molecular weight in the range of 2,000 to 25,000 g / mol, preferably in the range of 4,000 to 15,000 g / mol. An example of a suitable polyethylene glycol is PEG8000.

[0014] The hydrophilic portion of the associative thickener may be bonded to one or more coupling portions. The coupling portions may arise from a reactant containing two or more isocyanate groups (i.e., polyisocyanates). These reactants may be aliphatic, alicyclic, and / or aromatic isocyanates. Examples of polyisocyanates that can be used as coupling molecules include: 1,4-tetramethylene diisocyanate; 1,5-pentamethylene diisocyanate; 1,6-hexamethylene diisocyanate (HDI); 2,2,4-trimethyl-1,6-diisocyanatohexane; 2,4,4-trimethyl-1,6-diisocyanatohexane; 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate; 4,4'-methylenebis(isocyanatocyclohexane); 1,3-bis(2-isocyanatopropan-2-yl)benzene (TMXDI); 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane; m- and p-phenylenediisocyanate; 2,6- and 2,4-toluenediisocyanate (TDI); xylene diisocyanate; Examples include, but are not limited to, 4-chloro-1,3-phenylenediisocyanate; 4,4'-biphenylenediisocyanate; 4,4'-methylenedi(phenylisocyanate) ("MDI"); 1,5-naphthylenediisocyanate; 1,5-tetrahydronaphthylenediisocyanate; polymethylenepoly(phenylisocyanate); and isophorone diisocyanate (IPDI). Furthermore, dimers and trimers of these polyisocyanates (i.e., their uretdiones and isocyanurates) are also suitable polyisocyanates that can be used as reactants for preparing associative thickeners.

[0015] The polyisocyanate can contain any number of carbon atoms effective to provide the necessary degree of hydrophobicity. In some embodiments, the number of carbon atoms ranges from 4 to 30 atoms, or from 8 to 25, or from 10 to 20. In the case of uretdione dimers and isocyanurate trimers, the number of carbon atoms of the isocyanate preferably ranges from 10 to 50, preferably from 12 to 40, more preferably from 14 to 36. The number of carbon atoms can be selected based on the proportions of other hydrophobic and hydrophilic groups in the product.

[0016] In some embodiments, the polyisocyanate also includes any polyfunctional isocyanate derived from a reaction of any polyisocyanate with an active hydrogen compound having at least a functionality of 2 such that some isocyanate groups remain unreacted. Such isocyanates are similar to chain-extending an isocyanate-terminated isocyanate / diol reaction product with a reactant containing at least two active hydrogen atoms in a manner well-known in polyurethane synthesis.

[0017] In some embodiments, one or more coupling moieties of the associative thickener are bonded to one or more hydrophobic moieties. The hydrophobic moiety of a nonionic associative thickener (nonionic associative thickener) can contact and / or interact with the surface of particles in the application system.

[0018] For example, the hydrophobic moiety can interact with the surface of a filler used in a paint or the surface of latex particles.

[0019] In some embodiments, the associative thickener can be derived from one or more diisocyanate groups and / or isocyanurate trimer groups as coupling moieties. The isocyanate groups can be reacted with one or more hydrophilic moieties described herein.

[0020] In some embodiments, the above polyisocyanates can be used in combination with monoisocyanates. The monoisocyanates contain only one isocyanate group, and preferably these monoisocyanates contain one isocyanate group bonded to a hydrocarbyl group having 4 to 24 carbon atoms, more preferably to a hydrocarbyl group having 6 to 20 carbon atoms, for example, an alkyl or alkenyl group having 16 to 18 carbon atoms.

[0021] The at least one associative thickener includes at least one of the HEUR and HEAT thickeners.

[0022] Hydrophobically modified ethoxylated urethane thickeners (HEUR) are water-soluble polymers containing hydrophobic groups, which associate with each other in water, and are therefore classified as associative thickeners. In paint formulations, the hydrophobic groups can adsorb, for example, onto the surface of latex particles, thereby forming loops and crosslinks between the particles, creating a transient network of crosslinked latex particles that results in increased viscosity and desirable rheological properties over a wide range of shear rates.

[0023] Similarly, as described in US5,627,232A1 and US5,914,373A1, HEAT (hydrophobically modified ethoxylated aminoplast thickener), which is an aminoplast-ether copolymer containing aminoplast segments linked via ether segments, is classified as an associative thickener.

[0024] The hydrophobic portion of the associative thickener may include alkyl groups, arylalkyl groups, and aromatic groups, or combinations thereof. In the present invention, examples of hydrophobic portions include sterically hindered groups: more than one aromatic group bonded to a benzene ring.

[0025] Preferably, the associative thickener is an associative thickener according to formula (II): [ka] In the formula, R is at least one of a hydrophobic segment according to formula (I) and an aliphatic or alicyclic group having 7 to 20 carbon atoms, wherein at least one R is a hydrophobic segment according to formula (I); m is ≥ 1; n are independently ≥ 0; p is in the range of 45 to 500; R 5 However, it is selected from C2H4 and C3H6, however, R 5 At least 70 mol% of it is represented by C2H4; X is independently, [ka] And R 2 is aliphatic, alicyclic, or aromatic; or X is [ka] And, q ≥ 0, and R is as defined above; R 1 teeth: [ka] And R 3 These are aliphatic, alicyclic, or aromatic compounds.

[0026] Preferably, R in formula (II) not represented by formula I is an aliphatic or alicyclic group having 6 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and most preferably 9 to 18 carbon atoms.

[0027] In another embodiment, m is 1 to 10, more preferably 1 to 7, n is 0 to 40, more preferably 1 to 35, q is 0 to 40, more preferably 1 to 35, and p is 40 to 500, more preferably 100 to 300.

[0028] In a preferred embodiment, m is 1 to 4, n is 10 to 22, q is 10 to 22, p is 120 to 220, and R is a hydrophobic segment according to formula (I).

[0029] In a further embodiment, at least one X is

Chemical formula

[0030] In some embodiments, R 2 and / or R 3 is:

Chemical formula

[0031] In a further embodiment, R[[ID=3३]] 2 and / or R 3 is

Chemical formula

[0032] In all formulas, one or more bonds crossed by a wavy line indicate the bonding points of the structural segments to the parent structure.

[0033] The associative thickener can be prepared according to techniques generally known in the art for preparing urethanes such that substantially all of the isocyanate groups of the reactants react. In some embodiments, a solvent polymerization method known in the art can be used to prepare the associative thickener. In certain embodiments, a melt polymerization method known in the art can be used to prepare the associative thickener.

[0034] Preferably, at least one associative thickener has a number-average molecular weight Mn in the range of 4000 g / mol to 80000 g / mol. More preferably, at least one associative thickener has a number-average molecular weight Mn in the range of 5000 g / mol to 70000 g / mol, even more preferably, at least one associative thickener has a number-average molecular weight Mn in the range of 6500 g / mol to 60000 g / mol, and most preferably, at least one associative thickener has a number-average molecular weight Mn in the range of 8000 g / mol to 40000 g / mol.

[0035] The number-average molecular weight and weight-average molecular weight can be determined by gel permeation chromatography (eluent: THF, standard: polystyrene, column temperature: 25°C) according to DIN EN ISO 13885-1 (November 2021). Alternatively, the number-average molecular weight may be calculated.

[0036] The thickening agent composition according to the present invention contains an anionic surfactant. Examples of anionic surfactants include sulfosuccinates, alkyl (alkenyl) sulfates, alkyl (alkenyl) ether sulfates, ester sulfonates, soaps, and ether carboxylic acids.

[0037] Anionic surfactants useful in the present invention are characterized by having a hydrophilic solubilizing group that is a carboxylate, sulfonate, sulfate (sulfate group), or phosphate (phosphate group). These groups are preferably combined with a carbon chain hydrophobic group having 8 to 16 carbon atoms, which may optionally be alkoxylated. Preferably, the anionic surfactant contains at least one of alkyl ether sulfate, aryl ether sulfate, alkyl sulfate, aryl sulfate, or dialkyl sulfosuccinate.

[0038] In a preferred embodiment, the anionic surfactant has a sulfate group or a sulfate group. More preferably, the anionic surfactant has the following structure (III): R x -O-[R y -O] n -SO3 - M + (III)

[0039] In the formula, the counterion M + is Na + , K + , and NH + Selected from, R x This represents a tristyrylphenyl group or a C8-C20 alkyl or alkenyl group, more preferably a C9-C18 alkyl or alkenyl group, and even more preferably a C10-C16 alkyl or alkenyl group. R y This represents a group selected from C2H4 and C3H6, n is an integer between 0 and 35, preferably 1 and 30, more preferably 2 and 25, for example, between 3 and 20.

[0040] In an anionic surfactant of structure (III), R x It is highly preferable that this represents an alkyl group, most preferably a linear alkyl group.

[0041] All R y It is even more preferable that at least 50 mol%, preferably at least 70 mol%, and more preferably at least 90 mol%, of the group represent C2H4. In a very preferred embodiment, all of the group R y This represents C2H4.

[0042] It is even more preferable that n is an integer between 3 and 16.

[0043] Preferably, the anionic surfactant comprises at least one of tristyrylphenol ether sulfate, ammonium laureth sulfate, sodium laureth sulfate, sodium lauryl ether sulfate, ammonium lauryl ether sulfate, sodium alkylbenzene sulfonate, and sodium isotridecyl ether sulfate.

[0044] Preferably, the anionic surfactant is used in an amount of 5 to 65% by weight, more preferably 10 to 55% by weight, even more preferably 15 to 50% by weight, and most preferably 20 to 45% by weight, for example 25 to 40% by weight, calculated based on the total weight of the anionic surfactant and the associative thickener.

[0045] Preferably, the weight ratio of the associative thickener to at least one anionic surfactant is in the range of 19:1 to 7:13, calculated based on the total weight of the associative thickener and the anionic surfactant. More preferably, the weight ratio of the associative thickener to at least one anionic surfactant is in the range of 17:3 to 1:1, calculated based on the total weight of the associative thickener and the anionic surfactant, and even more preferably, it is in the range of 4:1 to 11:9, and most preferably, it is in the range of 3:1 to 3:2.

[0046] In preferred embodiments, the thickening agent composition comprises at least one nonionic surfactant. Nonionic surfactants, when dissolved in an aqueous medium, do not have discontinuous charges. The solubilizing groups in this type of surfactant are typically repeating units derived from alkylene oxides and hydroxyl groups. Examples of nonionic surfactants include alcohol alkoxylates, alkyl (poly)glycosides, and fatty acid ester alkoxylates. Another class of nonionic surfactants includes random, alternating, gradient, or block copolymers of different alkylene oxides, preferably ethylene oxide and propylene oxide, amine oxides, and gemini surfactants, as well as mixtures thereof.

[0047] Preferably, the nonionic surfactant comprises at least one of polyalkylene glycol monoalkyl ethers, polyalkylene glycols, and alkyl polyglycosides. Preferred polyalkylene glycols are copolymers of ethylene oxide and propylene oxide, very preferably random or block copolymers.

[0048] Preferably, the nonionic surfactant is used in an amount of 20-65% by weight, more preferably 25-60% by weight, even more preferably 28-55% by weight, and most preferably 32-50% by weight, for example, 35-45% by weight, calculated by the total weight of the nonionic surfactant, anionic surfactant and associative thickener.

[0049] The weight ratio of the associative thickener to at least one nonionic surfactant is preferably in the range of 7:3 to 1:3, calculated based on the total weight of the associative thickener and the nonionic surfactant. More preferably, the weight ratio of the associative thickener to at least one nonionic surfactant is in the range of 13:7 to 2:3, even more preferably in the range of 12:8 to 3:4, and most preferably in the range of 11:9 to 9:11, calculated based on the total weight of the associative thickener and the nonionic surfactant.

[0050] Preferably, the thickening agent composition contains 0 to 95% by weight of water, calculated based on the total weight of the composition. More preferably, the thickening agent composition contains 20 to 90% by weight of water, even more preferably 40 to 87% by weight of water, and most preferably 50 to 85% by weight of water, calculated based on the total weight of the thickening agent composition.

[0051] The thickening agent composition is preferably calculated based on the total weight of an associative thickening agent, an anionic surfactant, a nonionic surfactant, and water. 5.0-35.0% by weight of an associative thickener, 0.5-30.0% by weight of anionic surfactant, 0.0 to 30.0% by weight of nonionic surfactant, 5.0-94.5% by weight of water Includes.

[0052] The thickening agent composition is preferably calculated based on the total weight of the associative thickening agent, anionic surfactant, nonionic surfactant, and water. 7.5-30.0% by weight of an associative thickener, 1.0 to 25.0% by weight of anionic surfactant, 0.0 to 25.0% by weight of nonionic surfactants, 20.0-91.5% by weight of water Includes.

[0053] The thickening agent composition is more preferably calculated based on the total weight of the associative thickening agent, anionic surfactant, nonionic surfactant, and water. 10.0-25.0% by weight of an associative thickener, 2.5-22.0% by weight of anionic surfactant, 0.0 to 22.0% by weight of nonionic surfactant, 41.0-87.5% by weight of water Includes.

[0054] The thickening agent composition is very preferably calculated based on the total weight of an associative thickening agent, an anionic surfactant, a nonionic surfactant, and water. 12.0-20.0% by weight of an associative thickener, 5.0-10.0% by weight of anionic surfactant, 0.0 to 20.0% by weight of nonionic surfactant, 50.0-83.0% by weight of water Includes.

[0055] The thickening agent composition is appropriately calculated based on the total weight of the associative thickening agent, anionic surfactant, nonionic surfactant, and water. 5.0-35.0% by weight of an associative thickener, 0.5-30.0% by weight of anionic surfactant, 5.0-30.0% by weight of nonionic surfactant, 5.0-89.5% by weight of water Includes.

[0056] The thickening agent composition is very preferably calculated based on the total weight of an associative thickening agent, an anionic surfactant, a nonionic surfactant, and water. 12.0-20.0% by weight of an associative thickener, 5.0-10.0% by weight of anionic surfactant, 10.0-20.0% by weight of nonionic surfactant, 50.0-73.0% by weight of water Includes.

[0057] Preferably, the thickening agent composition does not contain or does not contain a polymeric film-forming binder. Furthermore, the thickening agent composition preferably does not contain or does not contain a pigment or pigment composition.

[0058] Furthermore, the present invention deals with liquid compositions comprising thickening agent compositions and binders according to the present invention. The term “liquid composition” according to the present invention means a composition that is liquid at 23°C and 10¹³ mbar.

[0059] Preferably, the liquid composition is an aqueous composition. The main or even sole liquid diluent of the aqueous composition is preferably water. Generally, the aqueous composition contains at least 10% by weight, preferably at least 20% by weight, and more preferably at least 30% by weight of water. Preferably, the aqueous composition contains 25-75% by weight of water, more preferably 30-65% by weight of water, and most preferably 35-55% by weight of water. In certain embodiments, the aqueous composition contains up to 95% by weight of water, or even up to 97%, 98%, or 99% by weight of water.

[0060] Preferably, the liquid composition is an aqueous coating composition. The aqueous coating composition can be prepared by dispersing or emulsifying a resin, or via emulsion polymerization. The resin used in the coating formulation may be insoluble in water, and the conversion of such a resin to an aqueous system typically involves converting the resin into an emulsion or dispersion.

[0061] The binder is a polymeric film-forming binder resin, which may be any resin known in the art. Preferably, it is a water-insoluble resin, such as a conventional natural or synthetic polymer latex.

[0062] Suitable binders include, but are not limited to, aqueous latex systems (typically obtained by emulsion polymerization), aqueous polyurethane resins (e.g., polyurethane dispersions and 2-pack systems), aqueous epoxy resins, aqueous alkyd resins (e.g., alkyd emulsions), aqueous polyester resins, and aqueous hybrid systems.

[0063] The main latex resins are based on homopolymers and copolymers of olefin monomers, and can be appropriately selected from: homopolymers of C2-C40 alpha-olefins; copolymers of ethylene, isobutylene, octene, nonene, or styrene with one or more esters; copolymers of ethylene, isobutylene, octene, nonene, or styrene with (meth)acrylic acid nitrile or amide; copolymers of ethylene, isobutylene, octene, nonene, or styrene with (meth)acrylic acid and its esters and amides; copolymers of ethylene, isobutylene, octene, nonene, or styrene with vinyl esters; copolymers of ethylene, isobutylene, octene, nonene, or styrene with vinylidene chloride; copolymers of ethylene, isobutylene, octene, nonene, or styrene with diene polymers, or mixtures thereof.

[0064] Examples of homopolymerized and copolymerized olefin monomers include, but are not limited to, vinyl acetate, vinyl chloride, styrene, butadiene, vinylidene chloride, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, acrylamide, methacrylamide, hydroxyethyl methacrylate (HEMA), glycidyl methacrylate, dihydroxypropyl methacrylate, vinyl acetate / butyl acrylate / 2-ethylhexyl acrylate, vinyl acetate / butyl maleate, vinyl acetate / ethylene, vinyl acetate / vinyl chloride / butyl acrylate, and vinyl acetate / vinyl chloride / ethylene, or mixtures thereof.

[0065] Examples of C2-C40 α-olefin homopolymers include, but are not limited to, ethylene, isobutylene, octene, nonene, styrene, or mixtures thereof. Examples of diene polymers, but are not limited to, include copolymers or mixtures thereof of butadiene with one or more esters of styrene, vinyltoluene, acrylonitrile, methacrylonitrile, and acrylic acid or methacrylic acid.

[0066] The liquid composition is preferably calculated based on the total weight of the associative thickener, anionic surfactant, and binder. 0.02 to 17.00% by weight of an associative thickener, 0.01 to 28.00% by weight of anionic surfactant, Binder resin with a weight of 55.00 to 99.97% Includes.

[0067] More preferably, the liquid composition is calculated based on the total weight of the associative thickener, anionic surfactant, and binder. 0.08-12.00% by weight of associative thickener, 0.03 to 20.00% by weight of anionic surfactant, Binder resin of 68.00 to 99.89% by weight Includes.

[0068] More preferably, the liquid composition is calculated based on the total weight of the associative thickener, anionic surfactant, and binder. 0.15-7.00% by weight of associative thickener, 0.06 to 12.00% by weight of anionic surfactant, Binders with a weight of 81.00 to 99.79% Includes.

[0069] The liquid composition is most preferably calculated based on the total weight of the associative thickener, anionic surfactant, and binder. 0.25-3.50% by weight of associative thickener, 0.10-3.50% by weight of anionic surfactant, Binder resin of 93.00 to 99.65% by weight Includes.

[0070] Liquid compositions may preferably contain one or more pigments and / or one or more pigment compositions or pigment concentrates. The term "pigment" refers to a substance that imparts color to another substance or mixture. Pigments usually exist in the form of organic or inorganic dry powders. "Pigment composition," "pigment paste," or "pigment concentrate" is also a substance that imparts color to another substance or mixture and generally contains at least one pigment and other additives. Dry pigments may be insoluble in organic solvents and water, which may require wetting, deaggregation, and deaggregation clumps before dispersion can occur and enable the production of stable colloidal pigment dispersions in paint formulations.

[0071] The liquid composition preferably contains one or more pigments and / or one or more pigment compositions. The pigment composition may contain white opaque pigments and / or colored pigments. Examples of colored pigments include organic pigments and inorganic pigments.

[0072] Pigment compositions, also called pigment pastes, preferably contain a wetting agent, a dispersant, a polyether, water, a neutralizing agent, an antifoaming agent, a preservative, and the like. Classes of compounds included in polyethers include polyalkylene glycols, e.g., low to medium molecular weight polyethylene and polypropylene glycol; polyhydroxy ethers, e.g., those formed from epoxide polymerization; polysaccharide compounds, e.g., polysorbitan and polysorbitol; and polyalkylene oxides, e.g., polyethylene and polypropylene oxide.

[0073] Examples of white opacifying pigments include, but are not limited to, rutile and anatase titanium dioxide, lithopone, zinc sulfide, lead titanate, antimony oxide, zirconium oxide, barium sulfide, white lead, zinc oxide, lead-containing zinc oxide, and mixtures thereof. In some embodiments, the average particle size of the opacifying pigment is in the range of 0.2 to 0.4 microns.

[0074] Examples of black pigments include, but are not limited to, various carbon blacks (Pigment Black 7), channel black, furnace black, lamp black, or mixtures thereof.

[0075] Pigments can also be selected from a wide range of conventional coloring pigments. Coloring pigments may be blue, black, brown, cyan, green, white, purple, magenta, red, orange, yellow, or mixtures thereof. Suitable classes of coloring pigments include, for example, anthraquinones, phthalocyanine blue, phthalocyanine green, diazos, monoazos, pyrantrones, perylenes, heterocyclic yellows, quinacridones, and (thio)indigoids. Representative examples of phthalocyanine blue include, but are not limited to, copper phthalocyanine blue and its derivatives (Pigment Blue 15).

[0076] Examples of quinacridone include Pigment Orange 48 and Pigment O Examples of range 49, iron oxide red, Pigment Red 122, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Violet 19, and Pigment Violet 42 are, but are not limited to these. Examples of anthraquinone-based pigments include, but are not limited to, Pigment Red 43, Pigment Red 194 (perinone red), Pigment Red 216 (brominated pyrantron red), and Pigment Red 226 (pyrantron red). Examples of perylene include, but are not limited to, Pigment Red 123 (vermilion), Pigment Red 149 (scarlet), Pigment Red 179 (maroon), Pigment Red 190 (red), Pigment Violet 19, Pigment Red 189 (yellowish red), and Pigment Red 224. Examples of thioindigoids include, but are not limited to, Pigment Red 86, Pigment Red 87, Pigment Red 88, Pigment Red 181, Pigment Red 198, Pigment Violet 36, and Pigment Violet 38. Examples of heterocyclic yellow pigments include, but are not limited to, Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 65, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 151, Pigment Yellow 117, Pigment Yellow 128, and Pigment Yellow 138. Such pigments are commercially available from many suppliers in either powder or pressed cake form.

[0077] Other examples of pigments include, but are not limited to, the following: Hostafine® Yellow GR (Pigment 13), Hostafine® Yellow (Pigment 83), Hostafine® Red FRLL (Pigment Red 9), Hostafine® Rubine F6B (Pigment 184), Hostafine® Blue 2G (Pigment Blue 15:3), Hostafine® Black T (Pigment Black 7), Hostafine® Black TS (Pigment Black 7), Normandy Magenta RD2400, Paliogen® Violet 5100, Paliogen® Violet 5890, Permanent Violet VT2645, Heliogen® Green L8730, Argyle Green XP-11-S, and Brilliant Green Toner GR. 0991, Heliogen(trademark) Blue D6900, L7020, Heliogen(trademark) Blue D6840, L7080, Heliogen(trademark) Blue D7101 F, Sudan Blue OS, PV Fast Blue B2GO1, Irgalite Blue BCA, Paliogen(trademark) Blue 6470, Sudan III, Sudan IV, Sudan Orange G, Sudan Orange 220, Paliogen(trademark) Orange 3040, Ortho(trademark) Orange OR 2673, Paliogen(trademark) Yellow 152, 1560, Lithol Fast Yellow 0991K, Paliotol Yellow 1840, Novoperm(trademark) Yellow FG 1, Permanent Yellow, Permanent Yellow YE 0305, (Lumogen Yellow) D0790, Suco-Gelb L1250, Suco-Yellow D1355, Hostaperm(TM) Pink E, Fanal Pink D4830, Cinquasia Magenta, LitholScarlet D3700, Toluidine Red, Scarlet for Thermoplast NSD PS PA, ED Toluidine Red, Lithol Rubine Toner, Lithol Scarlet 4440, Bon Red C, Royal Brilliant Red RD-8192, Oracet Pink RF, Paliogen® Red 3871K, Paliogen® Red 3340, and Lithol Fast Scarlet L4300.

[0078] In some embodiments, the aqueous coating composition is the paint composition. The paint composition can be prepared by mixing a base composition with one or more pigment compositions. The base composition may also contain other components such as water, polyglycol, latex resin, dispersant, defoamer, preservative, one or more opacifying pigments, binder, flocculant, and the thickening agent composition of the present invention.

[0079] The amount of the thickening agent composition in the paint may appropriately be in the range of 0.001g to 0.060g, 0.003g to 0.040g, or 0.005g to 0.020g per gram of the base paint, i.e., the paint before the addition of coloring materials.

[0080] The order in which the materials are mixed is carried out using methods known in the paint industry. For example, pulverized formulations and letdown formulations can be prepared. Pulverized formulations may include water, propylene glycol, cellulosic thickeners, dispersants, defoamers, preservatives, and TiO2. The pulverized formulations may be mixed and pulverized to disperse TiO2 in the formulation. Letdown formulations may include resins, opaque polymers, agglomerating compounds, associative thickeners, and / or defoamers. Letdown formulations can be added to pulverized formulations to form neutral-colored paint formulations. Pigments and / or pigment compositions can be added to neutral-colored paint formulations (base compositions) before painting and / or at the time of sale of the paint. One or more pigment compositions can be added to the base composition to impart color to the paint.

[0081] The associative thickeners described herein may also be used to improve the viscosity stability of other latex-free aqueous systems, such as cosmetics, hair dyes, aqueous cutting fluids, drilling fluids and fluids used in gas and oil production, packer fluids, cleaners, liquid detergents and fabric softeners, insecticides and agricultural compositions, personal care products (including shampoos, hair conditioners, hand lotions, hand creams, astringents, depilators and antiperspirants), and pharmaceutical formulations.

[0082] A further object of the present invention is to provide an article wherein at least a portion of the surface of the article is coated with a liquid composition. In different embodiments, the coated article can be obtained by the steps of providing an article, providing a liquid composition according to the present invention, and coating at least a portion of the surface of the article with the liquid composition.

[0083] In further embodiments, the present invention also relates to a method for improving the color viscosity stability of a liquid composition, comprising the steps of providing a liquid composition containing a binder, adding a thickening agent composition according to the present invention, mixing, adding one or more pigments and / or pigment compositions, and mixing. Suitable liquid compositions are, among other things, the liquid compositions described above. The step of mixing the components can be carried out according to current methods known to those skilled in the art. This may include, among other things, mixing by manual or electric means. Mixing involves combining the compositions and applying a shear force to the combined composition.

[0084] The present invention further relates to the use of a thickening agent composition according to the present invention for improving the color viscosity stability of a liquid composition having a pigment.

[0085] The present invention will be further described below with reference to the examples. For example, the selection of each reaction condition, such as reaction temperature, reaction time, and administration rate, is known to those skilled in the art and will be described in more detail in the examples.

[0086] Experiment Department Abbreviation: EO: Ethylene oxide PO: Propylene oxide IPDI: Isophorone diisocyanate TMDI: 2,2,4 (or 2,4,4)-trimethyl-1,6-diisocyanatohexane H12MDI: 4,4'-methylenebis(isocyanatocyclohexane) TMXDI: 1,3-Bis(2-isocyanatopropan-2-yl)benzene PEG: Polyethylene glycol

[0087] Formulation of thickening agent composition General instructions for preparing the thickening agent composition: Fill a glass bottle with water, sodium bicarbonate, biocide, and surfactant. Heat the mixture and stir until everything is completely dissolved. Add the associative thickener (polyurethane) and dissolve it under heating and stirring. Refer to Table 4 for the amounts used in specific examples.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] [Table 4]

[0092] [Table 5]

[0093] Test 1: Intake and Compatibility

[0094] [Table 6]

[0095] The water-based acrylic white paint was prepared using the formulations shown in Table 6. All given amounts are in weight percent. After preparation, the white paint was divided into smaller portions (50 g in a 175 ml PE beaker), and the sample of the present invention and the non-present invention were incorporated at a dose of 0.15% of the respective associative thickener (polyurethane) (calculated relative to the total lacquer) (see Table 6). The samples were added using a pipette under stirring conditions of 1000 rpm in a Dispermat LC3 (VMA Getzmann) using a 2.5 cm diameter toothed plate. The stirring time was 5 to 15 minutes at room temperature (23°C) until the sample became optically homogeneous. During product incorporation, it was evaluated whether the additives were easily added by dropping them into the paint via pipette, or whether addition was difficult due to threads formed during pipetting. After being stored overnight at room temperature (RT), the samples were applied to Bykochart 2851 (BYK-Gardner) with a wet film thickness of 120 μm using a flame film applicator (BYK-Gardner), and dried at room temperature for one day. As a criterion for determining suitability / workability, the seeding tendency was visually evaluated on a scale of 1 to 5 (none to strong seeding). Seeding is characterized by the appearance of aggregates of particles significantly larger than the thickness of the dry coating.

[0096] [Table 7]

[0097] Surprisingly, Examples IE1 to IE6 of the present invention were found to require significantly less incorporation time to produce a visually homogeneous formulation and to result in less seed and thread formation than comparative non-inventive example NE1; Example IE7 of the present invention resulted in significantly less seed in the final coating than comparative non-inventive example NE2; Example IE8 of the present invention resulted in less seed and thread than comparative non-inventive example NE3; and Example IE9 of the present invention resulted in less seed than comparative non-inventive example NE4 (see Table 7).

[0098] Test 2: Viscosity stability due to coloring with iron oxide red pigment concentrate

[0099] The water-based acrylic white paint was manufactured using the formulation shown in Table 8. All given amounts are in weight percent. After manufacturing, the white paint was divided into smaller portions (50 g in a 175 ml PE beaker), and the sample of the present invention and the non-present invention sample were incorporated at a dose of 0.15% of the associative thickener (polyurethane) (calculated relative to the total lacquer) (see Table 8). The sample of the present invention was added by pipette under stirring conditions of 1000 rpm using a Dispermat LC3 (VMA Getzmann) with a 2.5 cm diameter toothed plate. The stirring time was 5 to 15 minutes at room temperature (23°C) until the sample became optically homogeneous. After 1 day at room temperature, the viscosity of the white paint was measured using a rheometer MCR-301 (Anton Paar) at a shear rate of 1 s. -1 The viscosity was measured using controlled shear rate measurements. The red iron oxide pigment concentrate was prepared using the formulation shown in Table 9. The white paint was colored with the iron oxide pigment concentrate using a weight ratio of 95:5. After being stored overnight at room temperature, the viscosity of the colored paint was measured again.

[0100] To determine the change in viscosity due to coloring, the difference in viscosity between white lacquer and colored lacquer was calculated, and the percentage change compared to the initial viscosity of the white lacquer is shown in Table 10.

[0101] [Table 8]

[0102] [Table 9]

[0103] [Table 10]

[0104] As shown in Table 10, surprisingly, Examples IE1, IE3-IE6, and IE10-21 of the present invention were found to provide better viscosity stability when coloring with iron oxide red pigment concentrate than the comparative example non-inventive example NE1, which does not contain anionic surfactants. Similarly, Example IE9 of the present invention provides better viscosity stability when coloring with iron oxide red pigment concentrate than the corresponding non-inventive example NE4, which does not contain anionic surfactants.

[0105] Test 3: Viscosity stability due to coloring with green pigment concentrate

[0106] The water-based acrylic white paint was manufactured using the formulation shown in Table 11. All given amounts are in weight percent. After manufacturing, the white paint was divided into smaller portions (50 g in a 175 ml PE beaker), and the sample of the present invention and the sample of the non-present invention were added at a dose of 0.15% of the associative thickener (polyurethane) (calculated relative to the total lacquer) (see Table 4). The samples were added using a pipette under stirring conditions of 1000 rpm in a Dispermat LC3 (VMA Getzmann) using a toothed plate with a diameter of 2.5 cm. The stirring time was 5 to 15 minutes at room temperature (23°C) until the sample became optically homogeneous. After 1 day at room temperature, the viscosity of the white paint was measured by controlled shear rate measurement using a rheometer MCR-301 (Anton Paar) at 23°C, with a 2.5 cm 1° cone, for 1 second. -1 The measurements were then taken. Green pigment concentrates were prepared using the formulations shown in Table 12. The white paint was colored with the green pigment concentrate at a weight ratio of 95:5. After being stored overnight at room temperature, the viscosity of the colored paint was measured again. To determine the change in viscosity due to coloring, the difference in viscosity between the white lacquer and the colored lacquer was calculated, and the percentage change compared to the initial viscosity of the white lacquer is shown in Table 13.

[0107] [Table 11]

[0108] [Table 12]

[0109] [Table 13]

[0110] As shown in Table 13, surprisingly, Examples IE1, IE2, and IE6 of the present invention resulted in a reduction in viscosity loss during coloring, thereby providing better viscosity stability when adding pigment to the heliogen green pigment concentrate than the corresponding non-inventive example NE1, which does not contain an anionic surfactant. In the case of non-inventive example NE5, which contains an associative thickener structurally different from that of the present invention, the addition of an anionic surfactant (NE6) does not reduce the loss of coloring viscosity stability.

[0111] Test 4: Viscosity stability due to coloring with blue pigment concentrate

[0112] The water-based acrylic white paint was manufactured using the formulation shown in Table 14. All given amounts are in weight percent. After manufacturing, the white paint was divided into smaller portions (50 g in a 175 ml PE beaker), and the sample of the present invention and the sample of the non-present invention were added at a dose of 0.15% of the associative thickener (polyurethane) (calculated relative to the total lacquer) (see Table 4). The samples were added using a pipette under stirring conditions at 1000 rpm using a Dispermat LC3 (VMA Getzmann) with a 2.5 cm diameter toothed plate. The stirring time was 5 to 15 minutes at room temperature (23°C) until the sample became optically homogeneous. After 1 day at room temperature, the viscosity of the white paint was measured by controlled shear rate measurement using a rheometer MCR-301 (Anton Paar) at 23°C, with a 2.5 cm 1° cone, for 1 second. -1The measurements were then taken. Blue pigment concentrates were prepared using the formulations shown in Table 15. The white paint was colored with the blue pigment concentrate using a weight ratio of 95:5. After being stored overnight at room temperature, the viscosity of the colored paint was measured again. To determine the change in viscosity due to coloring, the difference in viscosity between the white lacquer and the colored lacquer was calculated, and the percentage change compared to the initial viscosity of the white lacquer is shown in Table 16.

[0113] [Table 14]

[0114] [Table 15]

[0115] [Table 16]

[0116] As shown in Table 16, surprisingly, Examples IE10-IE15 and IE17-IE22 of the present invention were found to provide better viscosity stability when coloring with blue pigment concentrates than comparative non-inventive example NE1, which does not contain anionic surfactants.

[0117] Test 5: Effects on gloss and color stability

[0118] The water-based acrylic white paint was prepared using the formulation shown in Table 17. All given amounts are in weight percent. After preparation, the white paint was divided into smaller portions (50 g in a 175 ml PE beaker), and the sample of the present invention and the sample not of the present invention were added at a dose of 0.15% of the associative thickener (polyurethane) (calculated relative to the total lacquer) (see Table 4). The samples were added using a pipette under stirring conditions at 1000 rpm in a Dispermat LC3 (VMA Getzmann) using a toothed plate with a diameter of 2.5 cm. The stirring time was 5 to 15 minutes at room temperature (23°C) until the sample became optically homogeneous. The red iron oxide pigment concentrate was prepared using the formulation shown in Table 18. The white paint was colored with the iron oxide pigment concentrate at a weight ratio of 95:5. After coloring, the paint was applied onto Bykochart 2851 (BYK-Gardner) using a 150 μm rod-shaped film applicator (BYK-Gardner). During drying, a typical rub-out test was performed, in which the paint was rubbed with a finger until the viscosity of the paint increased significantly and the pigment no longer lifted. After drying, gloss at 20° was measured using micro-Tri-gloss (BYK-Gardner), and the color difference, Delta E, between rubbed and unrubbed drawdowns was measured using a color guide (BYK-Gardner). In all cases, three measurements were taken and the average value was calculated.

[0119] [Table 17]

[0120] [Table 18]

[0121] [Table 19]

[0122] As shown in Table 19, surprisingly, Examples IE1 to IE5 of the present invention were found to produce higher gloss and lower color difference in the application system than the corresponding non-inventive example NE1. The same is observed in Example IE9 of the invention compared to the corresponding non-inventive example NE4. Non-inventive example NE7, which contains a non-inventive associative thickener, yielded inferior results to NE1, and the addition of an anionic surfactant (NE8) did not improve performance; in fact, the opposite effect was observed.

Claims

1. A thickening agent composition, At least one anionic surfactant, and At least one type of associative thickener Includes, The aforementioned associative thickener, - At least one polyether segment, and - At least one hydrophobic segment according to formula (I) 【Chemistry 1】 Includes, In formula (I), R ４ Each of these is independently hydrogen, alkyl, cycloalkyl, aryl, or arylalkyl, and the at least one associative thickener comprises at least one of HEUR and HEAT thickeners. Thickening agent composition.

2. The thickening agent composition according to claim 1, wherein the associated thickening agent is an associated thickening agent according to formula (II): 【Chemistry 2】 In formula (II), R is at least one of a hydrophobic segment according to formula (I) and an aliphatic group or alicyclic group having 7 to 20 carbon atoms, provided that at least one R is a hydrophobic segment according to formula (I); m is ≧1; n is each independently ≧0; p is in the range of 45 to 500; R ５ is C ２ H ４ and C ３ H ６ selected from, provided that at least 70 mol% of R ５ is represented by C ２ H ４ ; X is each independently, 【Transformation 3】 And in the formula, R ２ These are aliphatic, alicyclic, or aromatic groups; Or, X is 【Chemistry 4】 And, q is ≥ 0, and R is as defined above. R １ teeth: 【Transformation 5】 And R ３ These are aliphatic, alicyclic, or aromatic groups.

3. The thickening agent composition according to claim 1 or 2, wherein the at least one associative thickening agent has a number average molecular weight Mn in the range of 4,000 g / mol to 80,000 g / mol.

4. The thickening agent composition according to any one of claims 1 to 3, wherein the anionic surfactant comprises at least one of alkyl ether sulfate, aryl ether sulfate, alkyl sulfate, aryl sulfate, and dialkyl sulfosuccinate.

5. The thickening agent composition according to any one of claims 1 to 4, wherein the anionic surfactant comprises at least one of tristyrylphenol ether sulfate, laureth sulfate ammonium, laureth sulfate sodium, lauryl ether sulfate sodium, lauryl ether sulfate ammonium, alkylbenzene sulfonate sodium, and isotridecyl ether sulfate sodium.

6. The thickening agent composition according to any one of claims 1 to 5, wherein the weight ratio of the associated thickening agent and the at least one anionic surfactant is in the range of 19:1 to 7:13, calculated based on the total weight of the associated thickening agent and the anionic surfactant.

7. The thickening agent composition according to any one of claims 1 to 6, wherein the thickening agent composition comprises at least one nonionic surfactant.

8. The thickening agent composition according to claim 7, wherein the at least one nonionic surfactant comprises at least one of polyalkylene glycol monoalkyl ether, polyalkylene glycol, and alkyl polyglycoside.

9. The thickening agent composition according to any one of claims 1 to 8, wherein the thickening agent composition contains 0 to 95% water, calculated based on the total weight of the thickening agent composition.

10. A liquid composition comprising a thickening agent composition according to any one of claims 1 to 10 and a binder.

11. The liquid composition is calculated based on the total weight of the associative thickener, anionic surfactant, and binder. 0.02 to 17.00% by weight of the associated thickening agent, 0.01 to 28.00% by weight of the anionic surfactant, The binder in an amount of 55.00 to 99.97% by weight, The liquid composition according to claim 10, comprising:

12. A coated article wherein at least a portion of the surface of the article is coated with the liquid composition described in claim 10 or 11.

13. A method for improving the color viscosity stability of a liquid composition. - To provide a liquid composition containing a binder. - Adding the thickening agent composition described in any one of claims 1 to 9, - Mixing, - Adding one or more pigments and / or pigment compositions, - Mixing A method that includes the following steps.

14. Use of the thickening agent composition according to any one of claims 1 to 9 for improving the color viscosity stability of a liquid composition to which a pigment has been added.

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