Water-dispersible wax particles

Abstract

The present invention relates to a micronized wax composition, a method for producing the same, its use in the production of an aqueous formulation, an aqueous formulation containing the micronized wax composition, and a method for producing the aqueous formulation.

Description

Technical Field

[0001] The present invention relates to dispersible wax particles and micronized wax compositions, their use for producing aqueous formulations, aqueous formulations containing the micronized wax compositions, and methods for producing the aqueous formulations.

Background Art

[0002] Waxes and their derivatives are used in many industrial fields and households, especially in care products for the human body, such as cosmetics and hair care products, in care products for floors, furniture, clothing, shoes and automobiles, such as products as glazing agents and in foods, as well as in the production of plastic compositions, (hot melt) adhesives, printing inks, lacquers and other formulations.

[0003] Patent Document 1 (DE 10 2013007638) discloses a method for producing acidic wax from a mixture of natural wax and polyolefin wax, and a method for using it in soaps and shoe polishes.

[0004] Patent Document 2 (DE 102018116113) discloses oxidized natural wax used as a mold release agent or a brightening agent, especially in the production of shoe care products, automotive care products, floor care products, furniture care products, industrial mold release agents, coating compositions, hydrophobizing agents, adhesives, cosmetic compositions, production aids for plastic processing, and confectionery and chewing gum.

[0005] Liquid wax dispersions are used in the production of lacquers, printing inks, and other coating materials. However, organic solvents, which are not preferable from an economic and environmental perspective and often raise concerns about the health of humans and animals, are frequently used as the dispersion medium.

[0006] Patent Document 3 (EP-A 2970700) discloses a lacquer system containing chemically unmodified cellulose, polyolefin and / or Fischer-Tropsch and / or amide and / or biobased wax, and other components. This lacquer system has excellent scratch resistance and can be easily redispersed in butyl acetate even when the components of the lacquer settle. However, many of the described formulations contain organic solvents.

[0007] Due to this problem related to the use of organic solvents, aqueous wax dispersions are becoming increasingly important as a more cost-effective, environmentally friendly and less toxic alternative to solvent-containing dispersions.

[0008] Patent Document 4 (WO2006 / 131147) discloses a composition containing a bactericide and a wax or paraffin for use in aqueous paints. The composition is produced by melting the wax in an aqueous bactericide solution at 80°C to 85°C and then adding casein and a surfactant as thickeners to the mixture while paying attention to aggregation. The resulting formulation is added to an acrylic lacquer. Due to the high-temperature treatment and multiple-step process, the production of this wax dispersion is complex for inexperienced people and difficult to implement without the necessary expertise.

[0009] Patent Document 5 (DE4330342, BASF) discloses an aqueous polyolefin wax dispersion containing polyethylene or polypropylene wax, and glycerides reacted mainly with 1,2-alkylene oxides of unsaturated C16-22 monocarboxylic acids. These dispersions are produced by incorporating micronized wax into a dispersant solution in demineralized water.

[0010] The completed wax dispersion can be commercially sold and provided to users in a usable form. However, this often has a high water content and has the drawback that it requires a significantly larger volume for transportation and storage compared to selling the wax in solid form and having the user disperse it immediately before use. At the same time, the shelf life of aqueous wax dispersions is often shorter than that of solid waxes, and the stability of the dispersion is also limited, so the supplied dispersion needs to be used immediately after acquisition.

[0011] Therefore, there is a need for waxes that can be easily dispersed in aqueous formulations such as water or water-based lacquers and printing inks.

[0012] With easily dispersible wax particles, users can produce an aqueous wax dispersion on-site in their own facilities and use it immediately. This makes it possible to reduce transportation and storage costs, especially since only solid wax needs to be obtained.

[0013] Patent Document 6 (DE 10 2004059060) discloses the production and use of lipophilic waxes that can be easily stirred into oil-based paints and lacquers. No mention is made of dispersibility in water.

[0014] Patent Document 7 (DE 19620810) describes a mixture of non-functionalized polyethylene or polypropylene wax particles and a specific hydrophilic dispersant, which exists especially in the form of a flowable powder and is intended for the subsequent production of aqueous wax dispersions. These powders are a mixture of non-functionalized polyolefin waxes and glycerides (which may further contain hydroxyl groups) reacted with 1,2-alkylene oxides of mainly unsaturated C16-22 monocarboxylic acids. They are mixed without adding water. The resulting product is a flowable powder that can be easily incorporated upon addition of water. The conditions for dispersion production are not disclosed. This process requires a specific dispersant that is not necessarily suitable for all applications and requires knowledge about the production of wax dispersions that may not be accessible to some end users.

[0015] Patent Document 8 (US 2016018334) discloses the use of an O / W emulsion produced by the PIT process for lubricating conveyor belts in the food industry. Therefore, this document does not disclose micronized wax additives nor dispersions produced by dry grinding of waxes.

[0016] Patent Documents 9 (US 5746812) and 10 (WO2012022389) describe wax dispersions containing micronized waxes. These documents do not disclose that the wax is dry-ground together with an emulsifier.

[0017] Patent Document 11 (US20090294971) describes grinding wax dispersed with the help of an emulsifier using a MICROFLUIDIZER® processor to obtain a more stable dispersion. The dry grinding process and the products obtained by the dry grinding process are not disclosed.

[0018] Non-Patent Document 1 (Jian et al., J. Appl. Polymer Sc., 12 / 12 / 2012, 1476 - 1483) describes polyethylene wax (PEW) microspheres produced by a solution-precipitation process using PEW by-products as starting materials. The dry grinding process and the products obtained by the dry grinding process are not disclosed.

[0019] Patent Document 12 (DE 10 2015226240) describes rice bran wax bleached with an oxygen-containing gas and simultaneously polar-modified. These have the advantage of dispersing better in water and polar solvents compared to unmodified rice bran wax. However, the dispersion of such modified waxes requires knowledge and experience that may not necessarily be available to some end-users.

Prior Art Documents

Patent Documents

[0020]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Patent Document 10

Patent Document 11

Patent Document 12

Non-Patent Document

[0021]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0022] Therefore, there is still a need for a wax composition that can be rapidly and easily dispersed in aqueous formulations such as water and water-based lacquers and printing inks. This enables even inexperienced end-users to produce wax dispersions and also allows for easy modification of the finished product by mixing the compositions.

Means for Solving the Problems

[0023] Surprisingly, it has been found that by dry-grinding a wax in the presence of at least one emulsifier, a micronized wax composition that can be rapidly dispersed in water and aqueous formulations is obtained. For example, dispersion is also possible by stirring, shaking, or merely rocking. The rate of dispersion, avoidance of aggregates, and stability of the resulting dispersion are surprisingly significantly superior compared to the case where the wax and the emulsifier are mixed after completion of the grinding. In lacquers and coating materials, this micronized wax composition imparts good scratch resistance. Further, this micronized wax composition also exhibits good fluidity.

[0024] The present invention thus provides a method for producing a micronized wax composition (C), the production method being in the presence of at least one emulsifier (E), which is preferably in a liquid or dissolved state, and optionally, in the presence of at least one density additive (D) having a density > 1 g / cm 3 at 20 °C, where the density additive (D) is substantially insoluble in water at 20 °C, and optionally, in the presence of at least one wax (W), the at least one emulsifier (E), and at least one additional additive (A) different from the at least one density additive (D), comprising the step of dry-grinding at least one wax (W).

[0025] Grinding should be understood to mean dividing a solid material into smaller fragments through the action of mechanical force. Most grinding devices are designed for dry-grinding. Grinding of a paste into a liquid dispersion is known as wet-grinding (see Roempp, 9th edition).

[0026] Dry-grinding can heat the particles for grinding. If the heating becomes excessive, water can be used for cooling. However, grinding with cooling does not become equivalent to wet-grinding because the amount of water is reduced so as not to change the product characteristics. When dry-grinding is carried out in a mill, the emulsifier (E) is introduced into the grinding chamber through volume or weight input during the grinding of the wax (W).

[0027] In the present invention, the melting of the solid wax that is subsequently pulverized by spraying in a spray tower is also referred to as dry pulverization. The "dissolved state" means that the emulsifier is present in a highly concentrated state in the solvent, that is, the required amount of the emulsifier is completely dissolved and exactly enough solvent is used for the emulsifier to be sprayed or pump-injected. However, the amount of the solvent does not exceed 30% of the amount of the solvent required for complete dissolution.

[0028] This limitation of the amount of the solvent is necessary so that the micronized wax composition (C) cannot be obtained as a solid / solvent mixture (dispersion), the coating of the wax particles with the emulsifier is surely carried out, and the advantageous properties of the micronized wax composition are retained.

[0029] For dry pulverization, it is preferable to use water in an amount of less than 20% by weight, particularly preferably less than 10% by weight, and very particularly preferably less than 5% by weight, based on the total amount of the wax used for pulverization.

[0030] The present invention further provides a micronized wax composition (C) comprising the following: a) at least one wax (W); b) at least one emulsifier (E); c) optionally, at least one density additive (D) having a density at 20°C > 1 g / cm 3 , preferably > 1.3 g / cm 3 wherein the density additive (D) is substantially insoluble in water at 20°C; and, d) optionally, at least one additional additive (A) different from the at least one wax (W), the at least one emulsifier (E), and the at least one density additive (D); wherein the micronized wax composition (C) is obtained by dry pulverizing the at least one wax (W) in the presence of the at least one emulsifier (E), preferably in a liquid or dissolved state, optionally in the presence of the at least one density additive (D) and / or the at least one additional additive (A).

[0031] The water content of the micronized wax composition (C) is preferably less than 20% by weight, particularly preferably less than 10% by weight, and very particularly preferably less than 5% by weight, based on the total weight of the micronized wax composition (C). The water content is measured by analyzing a predetermined amount (2 - 7 g) of the sample (accuracy ±0.0001 g) at 105°C using an HR73 halogen moisture meter manufactured by Mettler Toledo. This measurement is carried out according to the manufacturer's specifications. If the weight loss is less than 1 mg after 90 seconds, the measurement is terminated after this time and the water content is determined. The micronized wax composition preferably consists of these components. Therefore, the wax composition (C) according to the present invention can be obtained by the process according to the present invention.

[0032] The expression "substantially insoluble in water at 20°C" should be understood to mean that at 20°C, at most 20 g, preferably at most 10 g, more preferably at most 5 g, and even more preferably at most 1 g of the density additive (D) can be dissolved in 1 L of water. As used herein, "micronized" means that the (average) particle size of the subject substance is smaller compared to its original state, and less than 1% by volume of the particles have a particle size of 1000 μm or more.

[0033] The particle size distribution can be measured, for example, by the laser diffraction method as described in "A Guidebook to Particle Size Analysis" (Horiba Instruments, Inc., 2019). Suitable measuring instruments for this purpose are, for example, LA - 960 manufactured by Horiba Instruments (which can measure particle sizes in the range of 10 nm - 5 mm), or Mastersizer 3000 manufactured by Malvern Panalytical (which can measure particle sizes in the range of 10 nm - 3.5 mm).

[0034] The micronized wax composition (C) preferably contains the following components: a) At least one wax (W) which is 40 to 99.9% by weight, preferably 50 to 99% by weight, more preferably 60 to 98.8% by weight, still more preferably 65 to 98.5% by weight, most preferably 70 to 98% by weight based on the weight of the micronized wax composition (C); b) At least one emulsifier (E) which is 0.1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1.2 to 8% by weight, still more preferably 1.5 to 5% by weight, most preferably 2 to 4% by weight based on the weight of the micronized wax composition (C); c) Optionally, at least one density additive (D) which is 0 to 59.9% by weight, preferably 0 to 45% by weight, more preferably 0 to 38% by weight, still more preferably 0 to 30% by weight, most preferably 0 to 26% by weight based on the weight of the micronized wax composition (C); and d) Optionally, at least one additional additive (A) which is 0 to 50% by weight, preferably 0 to 45% by weight, more preferably 0 to 38% by weight, still more preferably 0 to 30% by weight, most preferably 0 to 26% by weight based on the weight of the micronized wax composition (C).

[0035] It is preferred that the total amount of a), b), c) and d) is 100% by weight of the micronized wax composition (C), and the micronized wax composition (C) consists of the at least one wax (W), the at least one emulsifier (E), optionally the at least one density additive (D), and optionally the at least one additional additive (A).

[0036] When at least one density additive (D) is included, its amount is typically at least 0.1% by weight, preferably at least 1% by weight, more preferably at least 5% by weight based on the weight of the micronized wax composition (C). In these cases, the upper limit of the amount of wax (W) is adjusted so that the total of the components does not exceed 100% by weight.

[0037] When at least one additional additive (A) is included, its amount is typically at least 0.01% by weight, preferably at least 0.1% by weight, more preferably at least 1% by weight, based on the weight of the micronized wax composition (C). In these cases, the upper limit of the amount of wax (W) is adapted so that the total of the components does not exceed 100% by weight.

[0038] The present invention further provides an aqueous formulation which comprises water and, based on the total weight of the aqueous formulation, from 0.01% to 60% by weight, preferably from 0.1% to 50% by weight, more preferably from 0.2% to 4% by weight, or from 30% to 40% by weight, more preferably from 0.3% to 3% by weight, or from 32% to 38% by weight of the micronized wax composition (C), wherein the micronized wax composition (C) is dispersed in the water.

[0039] The present invention further provides a method for producing an aqueous formulation, comprising the following steps: i) preparing water, the micronized wax composition (C), and any additional components; ii) mixing the components prepared in step i), preferably by stirring, shaking or agitating.

[0040] The present invention further provides the use of the micronized wax composition (C) for producing an aqueous formulation, and the use of the micronized wax composition (C) according to the present invention and / or a wax concentrate obtained therefrom for improving the scratch resistance of a coating or lacquer produced from the ready-to-use aqueous formulation.

[0041] The micronized wax composition (C) according to the present invention and its components used in the production method according to the present invention will be described in detail below.

[0042] Wax (W) The wax (W) present in the micronized wax composition (C) may in principle be any desired wax. The wax (W) may for example be selected from the group consisting of synthetic organic waxes, semi-synthetic organic waxes, natural waxes (bio-based waxes) and mixtures thereof, and the wax may optionally be oxidized or otherwise chemically modified.

[0043] Suitable wax components are synthetic hydrocarbon waxes, such as polyolefin waxes. These can be produced by thermal decomposition of branched or unbranched polyolefin polymers or by direct polymerization of olefins. Suitable polymerization processes include for example free radical processes in which olefins, generally ethylene, are converted at high pressure and high temperature into polymer chains with greater or lesser degrees of branching, and processes in which ethylene and / or higher 1-olefins, such as propylene, 1-butene, 1-hexene etc., are polymerized using organometallic catalysts, such as Ziegler-Natta or metallocene catalysts, to obtain unbranched or branched waxes.

[0044] The corresponding processes for producing olefin homo- and copolymer waxes are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 28, Weinheim 1996, Chapter 6.1.1. / 6.1.2. (High-pressure polymerization (waxes)), Chapter 6.1.2. (Ziegler-Natta polymerization, polymerization with metallocene catalysts) and Chapter 6.1.4. (Thermal decomposition).

[0045] Furthermore, so-called Fischer-Tropsch waxes can be used. These are catalytically produced from synthesis gas and differ from polyethylene waxes by having a lower average molar mass, a narrower molar mass distribution and a lower melt viscosity. The hydrocarbon waxes used may be non-functionalized or may be functionalized with polar groups.

[0046] Such incorporation of polar functional groups can subsequently be effected by corresponding modification of the nonpolar wax, for example, by oxidation in air or by grafting onto polar olefin monomers such as α,β-unsaturated carboxylic acids and / or their derivatives such as acrylic acid or maleic anhydride. Polar waxes can be further produced by copolymerization of ethylene with polar comonomers such as vinyl acetate or acrylic acid, and by oxidative degradation of relatively high molecular weight non-waxy ethylene homopolymers and copolymers. Corresponding examples can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 28, 1996, Chapter 6.1.5.

[0047] Suitable polar waxes further include amide waxes that can be obtained, for example, by reacting longer-chain carboxylic acids such as fatty acids with monofunctional or polyfunctional amines. Fatty acids typically used for this purpose have a chain length in the range of 12 to 24, preferably 16 to 22 carbon atoms and can be saturated or unsaturated. Preferred fatty acids used include C16- and C18-acids, in particular palmitic acid and stearic acid or mixtures of both acids. Suitable amines other than ammonia include especially polyfunctional, for example bifunctional organic amines, with ethylenediamine being preferred. The use of waxes commercially available under the name EBS wax (ethylenebisstearoyldiamide) and produced from technical stearic acid and ethylenediamine is particularly preferred.

[0048] Furthermore, bio-based waxes, which are generally ester waxes, can be used. Generally, bio-based waxes mean waxes formed from a renewable raw material base. These can be either natural or chemically modified ester waxes. Typical natural bio-based waxes are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th indual, vol. A 28, 1996, chapter 2. These include palm waxes such as carnauba wax, candelilla wax, sugarcane wax, and grass waxes such as straw wax, beeswax, rice wax, and the like. Chemically modified waxes are usually formed from ester waxes or fatty acids based on vegetable oils by oxidation (e.g., by a mixture of CrO3 and H2SO4), esterification, transesterification, amidation, hydrogenation, etc. Examples of these also include metathesis products of vegetable oils.

[0049] Bio-based waxes further include montan waxes in their unmodified or purified / derivatized forms. Details of such waxes can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A 28, 1996, chapter 3 (Waxes).

[0050] Before dry grinding, the wax (W) can have any desired particle size. For example, the wax (W) may be granules having a particle size of >1 mm, for example 2 - 10 mm. However, before dry grinding, the wax (W) may have a particle size of ≦1 mm, for example 200 - 900 μm.

[0051] The micronized wax composition (C) according to the present invention exhibits good dispersibility in water and aqueous formulations such as aqueous lacquers and printing inks, even when the wax (W) itself does not essentially form a stable dispersion in water. Therefore, a functional group capable of enhancing the dispersibility of the wax is not required. However, the wax (W) may also contain a functional group that affects certain properties of the wax.

[0052] In one embodiment, the wax (W) does not essentially form a stable dispersion in water. As used herein, this means that after adding the wax (W) to water at 20°C (about 10% by weight of the wax), stirring is carried out for 5 minutes at a stirring speed of 700 rpm using a laboratory blade stirrer in the absence of an emulsifier, and phase separation can be visually confirmed within 1 hour.

[0053] In such an embodiment, preferably, the wax (W) is not oxidized and is not grafted or copolymerized with a heteroatom-containing group. It is preferred that the wax (W) in this embodiment does not contain a polar group.

[0054] Oxidation and grafting can have a positive effect on the dispersibility of the wax (W) in water and aqueous formulations, but they can also have an adverse effect on other properties of the wax. This embodiment is often related to synthetic or semi-synthetic waxes, particularly polyolefin waxes, whose properties are often adjusted by the selected synthesis conditions, and changing these properties is not desirable.

[0055] Such wax (W) preferably has an acid value (measured according to DIN EN ISO2114:2000), preferably a saponification value (measured according to DIN EN ISO3681:2018) and / or a hydroxyl value (measured according to DIN EN ISO2554:1997) of 0 to 40 mg KOH / g, preferably 0 to 20 mg KOH / g, more preferably 0 to 10 mg KOH / g, respectively. The polyolefin wax can be produced, inter alia, by Ziegler-Natta catalysis or metallocene catalysis, preferably metallocene catalysis, and preferably has an acid value of 0 to 5 mg KOH / g.

[0056] Waxes can generally be selected from polyolefin waxes, mineral waxes, montan waxes, rice bran waxes, beeswax, sunflower waxes, corn waxes, carnauba waxes, Fischer-Tropsch waxes, paraffin waxes, ester waxes and amide waxes. The wax is preferably selected from polyethylene wax, polypropylene wax, poly(ethylene co-propylene) wax, rice bran wax, corn wax and sunflower wax, more preferably HDPE wax (high density polyethylene).

[0057] The micronized wax composition (C) in which the pure wax (W) contains polar groups exhibits significantly improved dispersibility. Accordingly, in a further embodiment, the wax (W) may contain polar groups and may preferably be oxidized, grafted with heteroatom-containing groups, or chemically modified in other ways.

[0058] Oxidation is also relevant to natural waxes, especially montan wax, rice bran wax, sunflower wax, corn wax and carnauba wax, because these are typically dark in their raw state and can be bleached, for example, by oxidation. In the case of wax (W) containing polar groups, for example oxidized natural wax, the acid value is often greater than 15 mg KOH / g, preferably 20 to 200 mg KOH / g.

[0059] The acid value may be, for example, in the range of 45 to 70 mg KOH / g, or in the range of 70 to 170 mg KOH / g. Such waxes may also be further derivatized, for example, by esterification, amidation or saponification.

[0060] However, the wax (W) may be derivatized by other methods before micronization. For example, the wax, preferably a polyolefin wax, may be grafted with a heteroatom-containing group. These include, for example, waxes grafted with carboxylic acid derivatives having ethylenically unsaturated groups. Such derivatized waxes are preferably grafted with a heteroatom-containing group selected from acrylic acid, alkyl acrylates, acrylamides, methacrylic acid, alkyl methacrylates, methacrylamides, maleic acid, alkyl maleates, alkyl maleates, maleic anhydride and maleimides, more preferably maleic acid, maleic anhydride and maleimides, and most preferably maleic anhydride. The wax grafted with these functional groups is preferably a polyethylene wax, a polypropylene wax or a poly(ethylene co-propylene) wax, more preferably a polyethylene wax or a polypropylene wax, and most preferably an HDPE wax.

[0061] The wax (W) has a dropping point (measured according to DIN ISO 2176:1995) in the range of 100°C to 160°C, more preferably in the range of 110°C to 150°C, more preferably in the range of 120°C to 145°C, more preferably in the range of 125°C to 135°C, and has a density in the range of 0.88 to 1.06 g / cm 3 in the range, more preferably in the range of 0.90 to 1.02 g / cm 3 in the range, more preferably in the range of 0.90 to 1.00 g / cm 3 in the range, more preferably in the range of 0.90 to 0.98 g / cm 3 and is preferably a polyolefin wax having a density in the range.

[0062] Emulsifier (E) The emulsifier (E) can be any desired emulsifier that can improve the dispersibility of nonpolar solids in a polar medium, particularly in water. Suitable emulsifiers include nonionic, anionic, cationic, and amphoteric surfactants.

[0063] Suitable nonionic surfactants include, for example, fatty alcohol alkoxylates which may optionally have an alkyl end, fatty acid alkoxylates which may optionally have an alkyl end, alkyl glucosides, alkyl polyglucosides, alkylphenol ethoxylates, fatty acid esters of polyglycerol, and alkoxylated fatty acid glycerides. Preferred nonionic surfactants include C8 - C having 1 to 100, preferably 2 to 50, more preferably 3 to 10 alkylene oxide groups, preferably ethylene oxide and / or propylene oxide groups, more preferably ethylene oxide groups. 30 Fatty alcohol alkoxylates and C8 - C 30 Fatty acid alkoxylates are included.

[0064] Suitable anionic surfactants include, for example, fatty acid salts, alkylbenzene sulfonates, alkyl sulfonates, fatty alcohol sulfates, alkyl ether sulfates, sulfacetates, and taurides. Preferred anionic surfactants include alkali metal salts of C8 - C30 fatty acids, alkali metal salts of C8 - C30 alkylbenzene sulfonic acids, and alkali metal salts of C8 - C30 alkyl sulfonic acids.

[0065] Suitable cationic surfactants include, for example, quaternary ammonium salts, preferably halides, more preferably chlorides, for example, tetraalkylammonium salts having 1, 2, or 3 C8 - C 30 Alkyl groups and 3, 2, or 1 C1 - C4 alkyl groups, and quaternary ammonium salts of alkanolamine fatty acid esters (esterquats). Preferred cationic surfactants are C8 - C 30 Alkyltrimethylammonium salts, di(C8 - C30 (alkyl)dimethylammonium salts, and C8-C 30 It is an ester quat based on a quaternized triethanolamine ester having a fatty acid.

[0066] Suitable amphoteric surfactants include, for example, betaine derivatives containing a long-chain alkyl group, preferably a C5-C 30 alkyl group, and sulfobetaines containing a long-chain alkyl group, preferably a C5-C 30 alkyl group.

[0067] The emulsifier (E) is preferably a nonionic emulsifier, for example, a nonionic surfactant. It is more preferable when the emulsifier (E) is a nonionic emulsifier that is liquid at 20°C or water-soluble at 20°C.

[0068] The properties of nonionic emulsifiers can be represented, for example, by the mass ratio between the polar and nonpolar parts of the surfactant and are defined by the HLB value ("hydrophilic-lipophilic balance", the hydrophilic-lipophilic ratio of the molecule). The level of this hydrophilic-lipophilic ratio can be determined by calculating the values of different regions of the molecule as described by Griffin (see, for example, Journal of Society of Cosmetic Chemists, Vol. 5(4), pp. 249-256, 1954). The Griffin method was mainly developed for nonionic surfactants; the HLB value is calculated by the following formula. HLB = 20 * Mh / M (where Mh is the molecular mass of the hydrophilic part of the molecule and M is the molecular mass of the whole molecule, and the value is on a scale of 0 to 20.)

[0069] An HLB value of 0 represents a completely lipophilic molecule, and an HLB value of 20 represents a completely hydrophilic molecule.

[0070] The emulsifier (E) used in the production method according to the present invention and present in the wax composition (C) is preferably a nonionic emulsifier having an HLB value in the range of 6 to 16, preferably 7 to 15, more preferably 9 to 13, and even more preferably 10 to 12.

[0071] The emulsifier (E) is preferably present in the micronized wax composition (C) in an amount of 0.1 to 20% by weight, more preferably 1 to 15% by weight, more preferably 1.2 to 8% by weight, more preferably 1.5 to 5% by weight, and even more preferably 2 to 4% by weight based on the weight of the micronized wax composition (C).

[0072] Optional density additive (D) The micronized wax (C) may optionally contain a density additive (D) having a density at 20°C of > 1 g / cm 3 Preferably > 1.1 g / cm 3 More preferably 1.2 to 10.0 g / cm 3 More preferably 1.3 to 5 g / cm 3 More preferably 1.4 to 4.8 g / cm 3 The density additive (D) can be used to increase the density of the micronized wax composition (C), so that during dispersion in an aqueous solution, it does not float on the aqueous solution phase as much as possible. For this reason, the density additive (D) must be substantially insoluble in water at 20°C. Additives that dissolve easily in water increase the density of the aqueous phase and thus have the opposite effect.

[0073]

[0074] ​The amount of the density additive (D) in the micronized wax composition (C) is preferably selected such that the density of the micronized wax composition (C) is approximately equal to or slightly higher than the density of water. When the micronized wax composition (C) is dispersed in an aqueous solution having a density higher or lower than that of pure water, the amount of the density additive (D) can also be selected such that the density of the micronized wax composition (C) is approximately equal to or slightly higher than the density of the aqueous solution. The density additive (D) in the micronized wax composition (C) is such that the density of the micronized wax composition (C) at 20 °C is 0.94 - 1.20 g / cm 3 , preferably 0.96 - 1.10 g / cm 3 , more preferably 0.98 - 1.06 g / cm 3 , even more preferably 1.00 - 1.04 g / cm 3 and is preferably selected to be so.

[0075] The density additive (D) may be an organic additive or an inorganic additive. The organic density additive (D) can have a density of, for example, 1.1 - 2.8 g / cm 3 , preferably 1.3 - 2.5 g / cm 3 . Suitable organic density additives (D) include, inter alia, halogenated organic polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride and polytetrafluoroethylene (PTFE), polyamides and aramids as well as polysaccharides or polyglucosides such as cellulose, hemicellulose, starch, chitin, chitosan and the like. Preferred organic density additives (D) are PTFE wax and cellulose, more preferably PTFE wax.

[0076] The inorganic density additive (D) is, for example, 2.0 - 10.0 g / cm 3It can preferably have a density of 2.1 to 5.0 g / cm, more preferably 2.5 to 4.8 g / cm. Suitable inorganic density additives (D) include, among others, inorganic salts and minerals that are substantially insoluble. Examples of suitable inorganic density additives (D) are silicon dioxide, magnesium carbonate, magnesium fluoride, calcium carbonate, calcium sulfate, calcium fluoride, strontium carbonate, strontium sulfate, strontium fluoride, barium carbonate, barium sulfate, and barium fluoride. Preferred inorganic density additives (D) are sparingly soluble alkaline earth metal salts, more preferably calcium sulfate, calcium carbonate, barium sulfate, or barium carbonate, and even more preferably calcium carbonate.

[0077] Any additional additive (A) The micronized wax composition (C) may optionally contain at least one additional additive (A) that is different from the at least one wax (W), the at least one emulsifier (E), and the at least one density additive (D).

[0078] The additional additive (A) can be any desired additive that does not substantially affect the dispersibility of the micronized wax composition (C) in water. The additional additive (A) may include, for example, conventional wax additives that increase the stability of the wax against external influences. Suitable additional additives (A) include, for example, antioxidants, UV stabilizers, heat stabilizers, plasticizers, wetting aids, defoamers, processing aids, thixotropic agents, gelling agents, thickeners, mold release agents, flow control agents, fragrances, antibacterial agents, dyes, and pigments. In this specification, solvent residues such as water are also included in the additional additive (A). These may be present, for example, when at least one emulsifier (E) or additional additive (A) is used in a dissolved state.

[0079] When present, the additional additive (A) is used in the usual amounts of these additives. For example, the total amount of the additional additive (A) is 0.01% to 50% by weight, preferably 0.05% to 45% by weight, more preferably 0.1% to 38% by weight, more preferably 0.1% to 30% by weight, more preferably 0.1% to 26% by weight based on the weight of the micronized wax composition (C).

[0080] Method for producing the micronized wax composition (C) The micronized wax composition (C) is obtained by dry-grinding at least one wax (W) in the presence of at least one emulsifier (E). Any density additive (D) and / or any additional additive (A) may similarly be present during the dry-grinding or may simply be mixed with the micronized wax composition after the dry-grinding. It is preferable that at least any density additive (D), more preferably any additional additive (A) is also present during the dry-grinding of the wax (W).

[0081] In the dry-grinding of the at least one wax (W), the at least one emulsifier (E) may be present in a solid, liquid or dissolved state. When the emulsifier is in a solid state, usually, the wax (W) is mixed with the emulsifier (E) in a dry state and then ground together, or the solid emulsifier (E) is metered volumetrically or gravimetrically and fed into the grinding chamber during the grinding of the wax (W).

[0082] However, it is preferable that the at least one emulsifier (E) is in a liquid or dissolved state during the dry-grinding of the at least one wax (W). This often results in better dispersibility of the resulting micronized wax composition (C).

[0083] This means that when the emulsifier (E) is not in a dissolved state, the supply of the emulsifier (E) and the dry-grinding of the wax (W) in the presence of the emulsifier (E) are preferably carried out at a temperature exceeding the melting temperature of the emulsifier (E).

[0084] Thus, when the emulsifier is liquid at room temperature, as is the case with many non-ionic surfactants, the above supply and dry grinding can be carried out at room temperature. In the case of an emulsifier that is solid at room temperature but can be brought into a liquid state by melting, the dry grinding of the wax (W) can preferably be carried out at a correspondingly higher temperature.

[0085] In these cases, the melting temperature of the emulsifier (E) is preferably at least 10 °C lower than the melting temperature of the wax (W). Otherwise, partial softening / melting of the wax (W) may impair the dry grinding process.

[0086] Alternatively, the emulsifier (E) can also be used in a dissolved state, for example in an aqueous solution. This is particularly useful for emulsifiers (E) that have a high melting point and thus cannot be provided in liquid form without melting the wax (W), or that undergo thermal decomposition before the wax (W) is brought into a liquid state. This is the case for some ionic surfactants.

[0087] Providing the emulsifier (E) in a dissolved state can also be advantageous as it allows for better dispersion of the emulsifier (E). When providing the emulsifier (E) in a dissolved state, any density additive (D) and any additional additive (A) can also be dispersed or dissolved in the same solution and provided simultaneously. The emulsifier (E) is preferably provided as an emulsifier liquid at room temperature and / or as an aqueous solution. The emulsifier (E) is preferably introduced into the wax (W) by spraying it in a liquid or dissolved state during the grinding of the wax (W).

[0088] Dry grinding can preferably be carried out by any grinding method that enables dry grinding of the wax in the presence of the emulsifier (E) in a liquid or dissolved state. The micronized wax composition (C) after dry grinding has a volume median diameter D of 3 to 30 μm, more preferably 4 to 20 μm, more preferably 5 to 15 μm, more preferably 7 to 10 μm 50It is preferably the case of having [[measurement in water using Mastersizer 3000 of Malvern Panalytical]]. More preferably, at least 99% by volume of the particles of the micronized wax composition (C) have a size of at most 100 μm, more preferably at most 80 μm, more preferably at most 60 μm, and more preferably at most 30 μm after dry grinding.

[0089] Such particle sizes can be obtained using a suitable mill. Examples of such mills include impact mills, hammer mills, pin mills, and jet mills. It is preferable to use a mechanical impact mill or an air jet mill equipped with a classifier. Suitable mills and classifiers are commercially available, for example, from Hosokawa Alpine. The emulsifier (E) may be sprayed into the grinding chamber from a nozzle (in liquid or dissolved state), or may be filled together with the wax (W) first. Preferably, the emulsifier (E) is sprayed into the grinding chamber in liquid or dissolved state.

[0090] The above components in dry grinding are preferably as follows: a) The at least one wax (W) is 40 to 99.9% by weight, preferably 50 to 99% by weight, more preferably 60 to 98.8% by weight, still more preferably 65 to 98.5% by weight, and most preferably 70 to 98% by weight based on the weight of the components used; b) The at least one emulsifier (E) is 0.1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1.2 to 8% by weight, still more preferably 1.5 to 5% by weight, and most preferably 2 to 4% by weight based on the weight of the components used; c) Optionally, the at least one density additive (D) is 0 to 59.9% by weight, preferably 0 to 45% by weight, more preferably 0 to 38% by weight, still more preferably 0 to 30% by weight, and most preferably 0 to 26% by weight based on the weight of the components used; and d) Optionally, the at least one additional additive (A) is 0 to 50% by weight, preferably 0 to 45% by weight, more preferably 0 to 38% by weight, still more preferably 0 to 30% by weight, and most preferably 0 to 26% by weight, based on the weight of the components used.

[0091] a), b), c) and d) together total 100% by weight, and it is preferred that no further components are included. When the at least one density additive (D) is used, its amount is typically at least 0.1% by weight, preferably at least 1% by weight, more preferably at least 5% by weight, based on the total weight of the components used. In these cases, the upper limit of the amount of wax (W) used is adjusted so that the total of the components does not exceed 100% by weight.

[0092] The density additive (D) may be co-administered into the grinding chamber either on a volume basis or a weight basis, or premixed with the wax on a weight basis, to achieve a composition corresponding to the wax composition (C).

[0093] When at least one additional additive (A) is used, its amount is typically at least 0.01% by weight, preferably at least 0.1% by weight, more preferably at least 1% by weight, based on the total weight of the components used. In these cases, the upper limit of the amount of wax (W) used is adjusted so that the total of the components does not exceed 100% by weight.

[0094] The wax composition (C) according to the present invention can be used for producing an aqueous formulation. Surprisingly, the wax composition (C) according to the present invention has been found to disperse much faster in water or aqueous lacquer and aqueous ink than a similar composition in which the wax (W) is mixed with the emulsifier (E) only after micronization. Without being bound by a particular theory, dry grinding of the wax (W) in the presence of the emulsifier (E) results in more uniform wetting of the surface of the wax particles than in the case of mixing after micronization, and thus significantly promotes and accelerates its subsequent dispersion in water, and further, it is considered to enable reduction of the use of the emulsifier in the wax composition (C) according to the present invention.

[0095] The method for producing an aqueous formulation according to the present invention includes: i) a step of preparing water, the micronized wax composition (C) according to the present invention, and any additional components; ii) a step of mixing the components prepared in step i).

[0096] The provision of the micronized wax composition (C) according to the present invention in step i) can be carried out, for example, by grinding at least one wax (W) immediately before step ii) in the presence of at least one emulsifier (E), preferably in a liquid or dissolved state, and further optionally in the presence of at least one density additive (D) and / or at least one additional additive (A). Alternatively, storage of the micronized wax composition (C) may be carried out between dry grinding and mixing in step ii).

[0097] In this production method, the amounts of the micronized wax composition (C), water, and any additional components, and the types of any additional components are selected according to the desired concentrations in the aqueous formulation. This will be specifically described below.

[0098] Mixing can be carried out by any desired method. For example, mixing can also be carried out by stirring, shaking, or rocking the above components. Other mixing methods can also be used, for example, mixing using a static mixer that uses gas conduction or generation of turbulent flow by ultrasonic waves.

[0099] Stirring can be carried out, for example, using a mechanical stirrer such as a KPG stirrer, a hand mixer, a wand mixer, a blender, a disperser, a blade stirrer, a magnetic stirrer, or manually (for example, using a spatula or a spoon). Similarly, shaking and swinging can also be carried out manually or in an automated process. In this specification, "swing" represents a milder form of shaking, and the formation of bubbles by mixing with the gas phase is ideally avoided. For example, the vertical movement of the container or the mixing components is avoided as much as possible.

[0100] Suitable devices for shaking and / or swinging include, for example, shakers, rotators, bottle rollers, tumble mixers, and vibrating devices.

[0101] Preferably, the mixing is carried out by stirring or shaking, more preferably by stirring.

[0102] The aqueous formulation according to the present invention contains water and, based on the total weight of the aqueous formulation, 0.01 to 60% by weight, preferably 0.1 to 50% by weight, more preferably 0.2 to 4% by weight, or 30 to 40% by weight, more preferably 0.3 to 3% by weight, or 32 to 38% by weight of the micronized wax composition (C), and the micronized wax composition (C) is dispersed in water.

[0103] Furthermore, the aqueous formulation may contain additional components. These additional components can be selected as desired and are typically selected according to the end use of the aqueous formulation. Other components may contain the individual components of the micronized wax composition (C) in additional amounts. The additional components may include, for example, additional emulsifier (E), density additive (D), and / or additional additive (A), and these may already be present in the micronized wax composition (C).

[0104] The additional component may include, for example, stabilizers such as antioxidants, UV stabilizers and heat stabilizers, plasticizers, wetting aids, defoamers, processing aids, thixotropic agents, gelling agents, thickeners, fragrances, antibacterial agents, dyes and pigments, polymers, film-forming agents, fillers, resins and / or curing accelerators.

[0105] The aqueous formulation according to the invention may be an aqueous concentrate or may be a ready-to-use aqueous product such as, for example, an aqueous lacquer or an aqueous printing ink. The aqueous formulation is preferably an aqueous wax concentrate, an aqueous flexographic printing ink, an aqueous polyurethane lacquer or an aqueous acrylic lacquer.

[0106] As a wax concentrate, the aqueous formulation typically contains 20% to 60% by weight, preferably 25% to 50% by weight, more preferably 30% to 40% by weight, even more preferably 32% to 38% by weight of the micronized wax composition (C) based on the total weight of the aqueous formulation.

[0107] The wax concentrate preferably further contains at least one thickener selected from methylcellulose, xanthan gum, gelatin and agar, more preferably methylcellulose. The preferred amount of the thickener is typically 0.01% to 20% by weight, preferably 0.05% to 10% by weight, more preferably 0.1% to 1% by weight based on the total weight of the aqueous formulation.

[0108] In one embodiment, the aqueous formulation contains water, and 30% to 40% by weight, preferably 32% to 38% by weight, more preferably 34% to 36% by weight of the micronized wax composition (C) based on the total weight of the aqueous formulation, and a wax concentrate containing a thickener preferably selected from methylcellulose, xanthan gum, gelatin and agar, more preferably methylcellulose. The wax concentrate for general use consists of, for example, the micronized wax composition (C), water and a thickener and can be mixed with further components such as fragrances and dyes for the production of ready-to-use aqueous products.

[0109] As an aqueous product that can be used immediately, for example, as an aqueous lacquer or aqueous printing ink, the aqueous formulation typically contains, based on the total weight of the aqueous formulation, 0.01% to 20% by weight, preferably 0.05% to 15% by weight, more preferably 0.1% to 10% by weight, even more preferably 0.2% to 4% by weight, and even more preferably 0.3% to 3% by weight of the micronized wax composition (C). Such immediately usable aqueous solution products typically further contain additional components customary for specific types of products.

[0110] Aqueous products that can be used immediately, such as lacquers and printing inks, can be produced directly from the micronized wax composition (C) by mixing with water and further components, or can be obtained from a wax concentrate by mixing with further components. The wax concentrate or the micronized wax composition (C) can also be directly incorporated into the lacquer or printing ink, for example, to improve the scratch resistance of the immediately usable lacquer or printing ink.

[0111] The present invention is more specifically described by the following examples and claims.

Examples

[0112] Materials used: W1: Licowax® PE130GR (Clariant): HDPE wax granules having a particle size of about 7 mm, a dropping point of 127°C to 132°C, an acid value of 0 mg KOH / g, and a density of 0.96 to 0.98 g / cm 3 W2: Licocene® PE4201GR (Clariant): HDPE wax granules having a particle size of about 5 mm, a dropping point of 125°C to 130°C, an acid value of 0 mg KOH / g, and a density of 0.96 to 0.98 g / cm 3 ​​Micronized HDPE wax produced by dry grinding of W1 (not containing emulsifier and density additive) described in Production Example 1, having a W3:D50 value (volume median value) of 7.5 to 9.5 μm, a dropping point of 127°C to 132°C, an acid value of 0 mgKOH / g, and a density of 0.96 to 0.98 g / cm.

[0113] W4:Ceridust® 3715 (Clariant): Micronized oxidized HDPE wax having a D50 value of 7.5 to 9.5 μm, a dropping point of 122°C to 127°C, an acid value of 2 to 5 mgKOH / g, and a density of 0.96 to 0.98 g / cm 3 W5:Luwax® AF30 (BASF): Micronized HDPE wax having a D50 value of about 6.5 μm, a dropping point of 112°C to 120°C, an acid value of 1 to 3.6 mgKOH / g, and a density of 0.94 to 0.96 g / cm 3 W6:ACumist® A12 (Honeywell): Micronized oxidized HDPE wax having a D50 value of 10 to 13 μm, a dropping point of about 137°C, an acid value of 26 to 40 mgKOH / g, and a density of about 0.99 g / cm 3

[0114] W7:Ceridust® 1060Vita (Clariant): Micronized oxidized rice bran wax having a D50 value of 11 to 14 μm, a dropping point of 75 to 80°C, an acid value of 45 to 55 mgKOH / g, and a density of about 0.99 g / cm 3 W8:Licocare RBW102FL Vita (Clariant): Rice bran wax flakes having a flake diameter of 2 to 5 mm, a dropping point of 75 to 80°C, an acid value of 45 to 55 mgKOH / g, and a density of about 0.99 g / cm 3 W9:Ceridust® 1041Vita (Clariant): Micronized oxidized rice bran wax having a D50 value of 6 to 9 μm, a dropping point of 75 to 82°C, an acid value of 15 to 25 mgKOH / g, and a density of about 0.99 g / cm 3

[0115] E1: Nonionic emulsifier, a fatty alcohol polyglycol ether having an HLB value of about 11. E2: A plant-based nonionic emulsifier, palm fatty alcohol polyglycol ether having an HLB value of about 10 - 12. D1: D50 is about 5 μm, density 4.5 g / cm 3 of barium sulfate powder. D2: Median particle size 4 μm (measured according to ASTM D4894), density about 2.2 g / cm 3 of low molecular weight PTFE wax. D3: Density about 1.5 g / cm 3 of a polysaccharide mixture.

[0116] The particle size distribution was verified by laser diffraction (Mastersizer 3000, Malvern Panalytical, measured in water). For this purpose, a sample of the analyte was taken with a small measuring spoon (about 150 mg) and placed in a 50 ml beaker. 0.75 ml of a 5% aqueous solution of an emulsifier (nonylphenol polyglycol ether having 9 ethoxy groups) was added, and 3 drops of 2-propanol were added using a plastic pipette (3 ml with 0.5 ml graduations). 20 ml of deionized water was added, and the mixture was stirred with a blade stirrer at 1000 rpm for 3 minutes without the stirrer touching the walls of the beaker. After stirring, the sample was placed in a cooled ultrasonic bath for 3 minutes and then immediately examined by laser diffraction. The measurement was carried out according to the instruction manual of the equipment used (Mastersizer 3000, Malvern Panalytical).

[0117] Production Example 1 (of the present invention) To produce the micronized wax composition (C) according to the present invention, dry grinding of waxes [W1 (Licowax® PE130 granules), W8 (Licocare RBW102 FL VITA)] was carried out using a Zirkoplex classifier mill ZPS200 (Hosokawa Alpine) equipped with a classifier wheel, or an AFG200 fluidized bed counter jet mill (Hosokawa Alpine) equipped with an integrated classifier.

[0118] For dry grinding, first, the parameters of the device were adjusted so that the particle size distribution of the micronized wax had a D50 value in the range of 5 - 15 μm, a D90 value in the range of 10 - 40 μm, and a D99 value in the range of 15 - 70 μm, and it was carried out without an emulsifier. The material contained wax (W) and, when present, a density additive (D) as a solid mixture. The particle size distribution was verified by laser diffraction (Mastersizer 3000, Malvern Panalytical, measured in water) as described above. After obtaining the particle size distribution within the specific range, the parameters were kept constant.

[0119] To produce the wax composition (C), an emulsifier was sprayed laterally onto the grinding disk (ZPS200) or directly into the grinding chamber (AFG200) over a period of 5 - 40 minutes during grinding.

[0120] To produce the micronized wax W3, this process was carried out without a density additive (D) and without adding an emulsifier.

[0121] The conditions and results of dry grinding are shown in Table 1 (ZPS200) and Table 2 (AFG200).

Table 1

[0122]

Table 2

[0123] Production Example 2 (Comparative Example) The micronized wax W3 was blended with 3 wt% (Composition V1) or 18 wt% (Composition V2) of the emulsifier E1 (at 2000 RPM) using a Hausschild SpeedMixer® DAC150 (Hausschild GmbH & Co. KG) in the dry state.

[0124] Example 1 (Flowability) A down pipe (open glass cylinder; height 20 cm, diameter 1.5 cm) was placed on a black test mat, and the lower opening of the test mat was sealed with the test mat. 2.5 g each of the respective micronized wax compositions (Table 3) were filled into the down pipe from above. The down pipe was lifted to a distance of about 2 cm from the mat, and the wax powder fell to form a powder cone. The diameter of the obtained powder cone was measured with a ruler. A flatter and wider powder cone means better flowability. This test shows, firstly, that the flowability is better when the emulsifier content is low, and secondly, that the dry grinding of wax in the presence of an emulsifier gives better flowability than simply blending the emulsifier with the micronized wax after micronization.

[0125] [Table 3]

[0126] Example 2 (Dispersibility) 35 wt% of the micronized wax composition was dispersed in an aqueous solution containing 64.7 wt% of demineralized water, 0.1 wt% of a thickener (xanthan gum), 0.1 wt% of an antifoaming agent [Tego® Foamex 810, Evonik Industries], and 0.1 wt% of an antibacterial agent [Proxel® GXL, Arch Chemicals] (for 15 minutes at 1500 RPM), and the duration of dispersion stability was observed.

[0127] A stable dispersion containing wax W3 could be produced by the usual method only when the emulsifier E1 was first added to the aqueous solution and then only the micronized wax W3 was added. In contrast, the micronized wax compositions C1 - C according to the present invention 12 could be added directly to the aqueous solution without an additional initial charge of the emulsifier. The dispersion stability at room temperature is shown in Table 4.

[0128] [Table 4] (+: Stable; -: Separated)

[0129] When the amount of the emulsifier exceeded 2.5% by weight, the micronized wax composition (C) according to the present invention could be dispersed in water in a short time (<2 minutes) by shaking, manual stirring, or rocking each container.

[0130] The dispersion containing the compositions C9 - C11 containing the density additive (D) remained stable for a longer time and showed different phase separation behaviors after long - term storage (the solid did not float on the aqueous solution and, due to the increase in density, settled more deeply under the water surface). This is also more advantageous for redispersibility in the case of phase separation after long - term storage.

[0131] Example 3 (Dispersibility compared with polar - modified waxes) First, 90 g of deionized water was placed in a 250 - ml beaker, and 10 g of the micronized wax composition C4 or one of the polar waxes W4, W6, or W7 was added to the water surface. Then, a blade stirrer was immersed in the water until the distance to the bottom of the beaker was about a few millimeters.

[0132] The stirring operation was started at 700 rpm and then terminated after 5 minutes. Then, the blade stirrer was moved upward, and the mixture was observed. The observation was terminated after 2 hours.

[0133] In the micronized wax composition C4, wetting of the solid by water was observed from before the start of stirring. In waxes W4, W6, and W7, the waxes floated without visual wetting.

[0134] In the case of waxes W4, W6, and W7, immediately after the end of the stirring operation, the mixture completely separated into a clear water phase and the floating wax on it. In contrast, the micronized wax composition C4 formed a stable and homogeneous wax dispersion, and there was no visual change even after 2 hours.

[0135] Example 4 (Aqueous one - component polyurethane lacquer) First, an immediately available water-based one-component polyurethane lacquer (e.g., Bona Mega, Bona Vertriebsgesellschaft) was introduced, and the micronized wax composition or micronized wax was added slowly or rapidly, and using a laboratory disperser (Dispermat® LC30, VMA-Getzmann), it was mixed with the lacquer at 500 RPM for 0.5 minutes and then at 1000 RPM for 1 minute (total 1.5 minutes) to produce an aqueous formulation.

[0136] Next, the mixture was fixed between two slides (glass), and visible wax aggregates were counted. The results were as shown in Table 5.

[0137]

Table 5

[0138]

Table 6

[0139] For the comparative formulation, it was a homogeneous dispersion containing less than 50 detectable aggregates only at significantly high stirring speeds and significantly long dispersion times (20 minutes at 2000 RPM).

[0140] From these results, it is clear that the micronized wax composition (C) according to the present invention can be incorporated into an aqueous lacquer much more rapidly and much more uniformly than commercially available (unmodified and modified) waxes, or when an emulsifier is added only after micronization (V1, V2).

[0141] Similar results are also seen for one-component acrylic lacquers and printing inks for flexographic printing.

[0142] Example 5 (Scratch resistance of lacquer) A one-component polyurethane lacquer was produced in the same manner as in Example 4, and dispersion was carried out at 2000 RPM for 20 minutes. In order to mix them homogeneously in Comparative Examples W3 and W4, the dispersion time was set to 20 minutes. With a shorter dispersion time, these would form aggregates in the lacquer, and the lacquer surface to be tested would likewise be non-uniform, and thus could not be tested. The wax composition (C) of the present invention can still be tested even after being added according to Example 4.

[0143] The formulations were applied to glass plates, cured, and their scratch resistance was examined. This was carried out using the pencil scratch hardness test method (DIN EN ISO1518-1:2019) and the Schmiss test (ASTM5178-21). The results are shown in Table 6.

[0144]

Table 7

[0145] A one-component acrylic lacquer containing the micronized wax / wax composition was produced in a similar manner, and its scratch resistance was examined according to DIN EN ISO1518-1:2019. The results are shown in Table 7.

[0146]

Table 8

[0147] It is clear from the results that the lacquer containing the micronized wax composition (C) of the present invention has scratch resistance equivalent to or higher than that of lacquers having commercially available (unmodified and modified) waxes.

Claims

1. In the presence of at least one emulsifier (E) and, optionally, in the presence of at least one density additive (D) having a density > 1 g / cm at 20°C, where the density additive (D) is substantially insoluble in water at 20°C and, optionally, in the presence of at least one wax (W), the at least one emulsifier (E), and at least one additional additive (A) different from the at least one density additive (D), a method for producing a micronized wax composition (C) comprising a step of dry-grinding at least one wax (W). ３ ​

2. The grinding is carried out using less than 20% by weight of water, based on the amount of wax (W) used for grinding, according to the manufacturing method of Claim 1.

3. In the grinding, the at least one emulsifier (E) is present in a liquid or dissolved state, according to the manufacturing method of Claim 1 or 2.

4. The wax (W) does not essentially form a stable dispersion in water, according to the manufacturing method of any one of Claims 1 to 3.

5. The density additive (D) is an organic additive, preferably selected from halogenated organic polymers and polysaccharides, more preferably selected from polytetrafluoroethylene wax, cellulose, and hemicellulose, and / or an inorganic additive, preferably selected from salts, more preferably selected from alkaline earth metal salts, and even more preferably selected from calcium sulfate, calcium carbonate, barium sulfate, and barium carbonate, according to the manufacturing method of any one of Claims 1 to 4.

6. The following amounts of components are used for the grinding: a) The at least one wax (W) is 40 to 99.9% by weight, preferably 50 to 99% by weight, more preferably 60 to 98.8% by weight, even more preferably 65 to 98.5% by weight, and most preferably 70 to 98% by weight, based on the weight of the components used; b) The at least one emulsifier (E) is 0.1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1.2 to 8% by weight, even more preferably 1.5 to 5% by weight, and most preferably 2 to 4% by weight, based on the weight of the components used; c) Optionally, the at least one density additive (D) is 0 to 59.9% by weight, preferably 0 to 45% by weight, more preferably 0 to 38% by weight, even more preferably 0 to 30% by weight, and most preferably 0 to 26% by weight, based on the weight of the components used; and d) Optionally, the at least one additional additive (A) is 0 to 50% by weight, preferably 0 to 45% by weight, more preferably 0 to 38% by weight, even more preferably 0 to 30% by weight, and most preferably 0 to 26% by weight, based on the weight of the components used, according to the manufacturing method of any one of Claims 1 to 5.

7. The wax (W) is selected from the group consisting of synthetic organic waxes, semi-synthetic organic waxes, natural waxes, and mixtures thereof, wherein the wax is optionally oxidized or chemically modified in other ways, preferably a polyolefin wax, montan wax, rice bran wax, beeswax, sunflower wax, corn wax, carnauba wax, Fischer-Tropsch wax, paraffin wax, ester wax, and amide wax, more preferably selected from polyethylene wax, polypropylene wax, poly(ethylene co-propylene) wax, rice bran wax, corn wax, and sunflower wax, and even more preferably HDPE wax, the production method according to any one of claims 1 to 6.

8. The emulsifier (E) is introduced into the wax (W) by spraying it in a liquid or dissolved state during the grinding of the wax (W), the production method according to any one of claims 1 to 7.

9. The wax (W) is not oxidized and not grafted with a heteroatom-containing group, preferably does not contain a polar group, the production method according to any one of claims 1 to 8.

10. The wax (W) contains a polar group, preferably is oxidized or grafted with a heteroatom-containing group, the production method according to any one of claims 1 to 9.

11. The amount of the density additive (D) is such that the density of the micronized wax composition (C) at 20 °C is 0.94 to 1.20 g / cm ３ , preferably 0.96 to 1.10 g / cm ３ , more preferably 0.98 to 1.06 g / cm ３ , still more preferably 1.00 to 1.04 g / cm ３ and is selected so as to be in the range, and is a production method according to any one of claims 1 to 10.

12. The wax (W) is ground so that the volume median particle size D50 is in the range of 3 to 30 μm, preferably 4 to 20 μm, more preferably 5 to 15 μm, and even more preferably 7 to 10 μm, the production method according to any one of claims 1 to 11.

13. a) at least one wax (W); b) at least one emulsifier (E); c) Optionally, at least one density additive (D) having a density at 20 °C > 1 g / cm ３ wherein the density additive (D) is substantially insoluble in water at 20 °C; and d) optionally, at least one additional additive (A) different from the at least one wax (W), the at least one emulsifier (E), and the at least one density additive (D), comprising (preferably consisting of) a micronized wax composition (C), wherein the micronized wax composition (C) is obtained by the production method according to any one of claims 1 to 12, the micronized wax composition (C).

14. The water content of the micronized wax composition (C) is less than 20% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight, based on the total weight of the micronized wax composition (C), as measured by an HR73 moisture meter manufactured by METTLER TOLEDO. The micronized wax composition (C) according to claim 13.

15. a) The at least one wax (W) is 40 to 99.9% by weight, preferably 50 to 99% by weight, more preferably 60 to 98.8% by weight, still more preferably 65 to 98.5% by weight, most preferably 70 to 98% by weight, based on the weight of the micronized wax composition (C); b) The at least one emulsifier (E) is 0.1 to 20% by weight, preferably 1 to 15% by weight, more preferably 1.2 to 8% by weight, still more preferably 1.5 to 5% by weight, most preferably 2 to 4% by weight, based on the weight of the micronized wax composition (C); c) Optionally, the at least one density additive (D) is 0 to 59.9% by weight, preferably 0 to 45% by weight, more preferably 0 to 38% by weight, still more preferably 0 to 30% by weight, most preferably 0 to 26% by weight, based on the weight of the micronized wax composition (C); and d) Optionally, the at least one additional additive (A) is 0 to 50% by weight, preferably 0 to 45% by weight, more preferably 0 to 38% by weight, still more preferably 0 to 30% by weight, most preferably 0 to 26% by weight, based on the weight of the micronized wax composition (C), The micronized wax composition (C) according to claim 13 or 14.

16. An aqueous formulation comprising water and 0.01 to 60% by weight, preferably 0.1 to 50% by weight, more preferably 0.2 to 4% by weight or 30 to 40% by weight, still more preferably 0.3 to 3% by weight or 32 to 38% by weight, of the micronized wax composition (C) according to any one of claims 13 to 15, wherein the micronized wax composition (C) is dispersed in the water.

17. The aqueous composition contains a wax concentrate, and the wax concentrate contains water and, based on the total weight of the aqueous composition, 30 to 40% by weight, preferably 32 to 38% by weight, more preferably 34 to 36% by weight of micronized wax (C), and a thickener, preferably a thickener selected from methylcellulose, xanthan gum, gelatin and agar, more preferably methylcellulose. The aqueous composition according to claim 16.

18. The aqueous composition is an aqueous printing ink or an aqueous lacquer, preferably an aqueous flexographic printing ink, an aqueous polyurethane lacquer or an aqueous acrylic lacquer. The aqueous composition according to claim 16.

19. i) A step of preparing water, the micronized wax composition (C) according to any one of claims 13 to 15, and optionally additional components; ii) A step of mixing the components prepared in step i), preferably by stirring, shaking or oscillating. A method for producing an aqueous composition, comprising:

20. The preparation of the micronized wax composition (C) by grinding at least one wax (W) in the presence of at least one emulsifier (E) in step i), preferably in a liquid or dissolved state, and optionally in the presence of at least one density additive (D) and / or at least one additional additive (A), is carried out immediately before step ii) or includes storage during the grinding and mixing in step ii). The production method according to claim 19.

21. Use of the micronized wax composition (C) according to claims 13 to 15 for the production of an aqueous composition.

22. Use of the micronized wax composition (C) according to claims 13 to 15 and / or a wax concentrate obtained therefrom for improving the scratch resistance of a coating film produced with an aqueous composition.

Images