Comb polymers with salt groups

Abstract

The present invention relates to a comb polymer having a polymer backbone and side branches attached to the polymer backbone, wherein the side branches comprise a) alkyl ether end-capped polyoxyalkylene branches, and b) tertiary amine functional branches, wherein the tertiary amine groups are at least partially neutralized with an acid having a molecular weight of 100 g / mol to 2000 g / mol, wherein in case the acid is a polymeric acid, the molecular weight relates to the number average molecular weight Mn, and the side branches a) and b) are distributed in a random fashion.

Description

[0001] This invention relates to a comb-shaped polymer having alkyl ether-terminated polyoxyethylene branches and neutralized tertiary amine functional branches, to compositions comprising the comb-shaped polymer and at least one colorant, and to the use of the comb-shaped polymer as a wetting agent and / or dispersant for solid particles.

[0002] US 7078464 describes compositions comprising an amine-functionalized unsaturated carboxylate of a styrene-maleic anhydride copolymer. The use of this composition as a pigment dispersant is also described. Preferred unsaturated carboxylic acids are acrylic acid and methacrylic acid.

[0003] WO 2008 / 080580 describes a modified comb copolymer prepared by reacting SMA resin with polyoxyethylene monoamine and primary and tertiary diamines. The tertiary amine groups are at least partially converted to quaternary ammonium salts. The modified comb copolymer is suitable for use as a pigment dispersant resin.

[0004] WO 2013 / 189568 describes copolymers and their use as wetting and dispersing agents. These copolymers are prepared by reacting a main-chain polymer with a primary amine or primary alcohol, each having at least one tertiary amine group, followed by quaternization. In some embodiments, the main-chain polymer may be modified with a polyoxyethylene monoamine.

[0005] There remains a need for polymers suitable for use as wetting and dispersing agents, offering improved properties to both aqueous and organic solvent-based pigment dispersions. In particular, pigment dispersions with low viscosity, excellent storage stability, and broad compatibility with various types of binders used in coating compositions and other coloring compositions are required. Pigment dispersions for the production of color resists for flat panel displays need to provide improved color-developing properties and good resolubility. The polymer should be readily prepared from available raw materials, preferably without the need for sensitive polymerization techniques.

[0006] This invention provides a comb-shaped polymer having a polymer backbone and side branches connected to the polymer backbone, wherein the side branches comprise:

[0007] a) Alkyl ether-terminated polyoxyethylene branches, and

[0008] b) A tertiary amine functional branch, wherein the tertiary amine group is at least partially neutralized by an acid with a molecular weight of 100 g / mol to 2000 g / mol, wherein, if the acid is a polymeric acid, the molecular weight relates to the number average molecular weight Mn.

[0009] Furthermore, the side branches a) and b) are distributed in a random manner.

[0010] The comb-shaped polymer of this invention is suitable for use as a wetting and dispersing agent, and provides improved properties to aqueous pigment dispersions and organic solvent-based pigment dispersions. Pigment dispersions obtained from the comb-shaped polymer exhibit low viscosity, excellent storage stability, and broad compatibility with various types of binders used in coating compositions and other coloring compositions. Improved color development properties and excellent resolubility are observed when used in pigment dispersions for the production of color photoresists for flat panel displays. This polymer is readily prepared from available raw materials and does not require the use of sensitive polymerization techniques.

[0011] The polymers of the present invention comprise a polymer backbone. The polymer backbone is a linear or branched polymer having repeating units. Preferably, the polymer backbone has a substantially linear or fully linear structure. Generally, there are no particular limitations on the type of polymer forming the polymer backbone, and it can be selected from polymer types known to those skilled in the art. Examples of suitable polymer types include polyesters, polyurethanes, polycarbonates, and polymers and copolymers of polymerizable olefinic unsaturated monomers. With regard to a wide variety of available olefinic unsaturated monomers having other functional groups, polymers and copolymers of these monomers, collectively referred to as (co)polymers, are preferably used as the polymer backbone. Examples of suitable olefinic unsaturated monomers are vinyl esters, vinyl ethers, vinyl aromatic compounds such as styrene, acrylic acid and methacrylic acid, and their esters and amides, collectively referred to as (meth)acrylates. Suitable monomers also include maleic acid and fumaric acid, and their derivatives, such as anhydrides, esters, amides, and imides.

[0012] In a preferred embodiment, the polymer backbone comprises polymerization units of vinyl aromatic monomers, particularly styrene polymerization units.

[0013] It is also preferred that the polymer backbone comprises N-substituted maleimide polymeric units. Particularly preferred is that the side branches a) and b) are attached to the polymer via nitrogen atoms in the N-substituted maleimide polymeric units.

[0014] In the polymers of this invention, side branches are connected to the polymer backbone. Typically, the side branches are covalently connected to the polymer backbone. The resulting structure can also be referred to as a comb-shaped polymer.

[0015] Typically, two or more side chains are covalently attached to the polymer backbone.

[0016] The side chains include alkyl ether-terminated polyoxyethylene side chains.

[0017] The alkyl ether typically comprises an alkyl group having 1 to 32 carbon atoms. The alkyl group can be straight-chain or branched. The alkyl group may also contain cyclic groups. In a preferred embodiment, the alkyl group has 1 to 8 carbon atoms.

[0018] The polyoxyolefin groups typically have a number-average molecular weight of 88 to 5000 g / mol. In a preferred embodiment, the number-average molecular weight is 132 to 4000 g / mol, more preferably 132 to 2000 g / mol, and the number-average molecular weight can be determined by gel permeation chromatography.

[0019] The polyoxyolefin group comprises polymeric units of olefin oxides. The olefin oxides are preferably selected from ethylene oxide, propylene oxide, and combinations thereof. Particularly preferred is that the polyoxyolefin group comprises or is composed of polymeric units of ethylene oxide. If the polyoxyolefin branch comprises polymeric units of more than one type of olefin oxide, these units may be arranged statistically, as a gradient, or in a block arrangement. The number of polymeric olefin oxide units in the polyoxyolefin branch is typically in the range of 1 to 114, for example, 3 to 91, or 4 to 45.

[0020] In one embodiment, each branch has the same type of alkyl ether-terminated polyoxyethylene groups. In other embodiments, branches with different types of these groups may be present.

[0021] Side chains containing alkyl ether-terminated polyoxyethylene groups are typically connected to the polymer backbone via linking groups. Suitable examples of linking groups are ester groups, amide groups, and imide groups. In a preferred embodiment, the alkyl ether-terminated polyoxyethylene side chains are connected to the polymer backbone via imide groups.

[0022] The comb-shaped polymer of the present invention further comprises tertiary amine functional side chains. The tertiary amine functional side chains comprise tertiary amine groups. Typically, these side chains contain one tertiary amine group per side chain. The tertiary amine group comprises a straight-chain, branched, or cyclic alkyl group attached to the amine nitrogen. In typical embodiments, the alkyl group has 1 to 18 carbon atoms per alkyl group, preferably 1 to 8 carbon atoms. In some embodiments, the alkyl group may form a cyclic structure with the amine nitrogen.

[0023] Side chains containing tertiary amine groups are typically attached to the polymer backbone via linking groups. Suitable examples of linking groups are ester groups, amide groups, and imide groups. In a preferred embodiment, the tertiary amine-functionalized side chains are attached to the polymer backbone via imide groups.

[0024] The amount of tertiary amine groups in the comb-shaped polymer of the present invention is typically chosen to give the comb-shaped polymer an amine value in the range of 5 to 150 mg KOH / g. Preferably, the amine value is at least 10 mg KOH / g, more preferably at least 15 mg KOH / g. Preferably, the amine value of the comb-shaped polymer is at most 120 mg KOH / g, more preferably at most 100 mg KOH / g. The amine value relates to the non-volatile content of the comb-shaped polymer. In a very preferred embodiment, the amine value of the comb-shaped polymer is in the range of 15 to 100 mg KOH / g.

[0025] The side branches a) of the polyalkylene group containing alkyl ethers and the side branches b) containing tertiary amine groups are distributed randomly. This means that these side branches a) and b) are arranged along the polymer backbone without a specific order or structure, which is the opposite of block copolymers, in which a specific structure exists in the identifiable segments of the copolymer but not in other segments.

[0026] In the comb-shaped polymer of the present invention, the tertiary amine groups are at least partially neutralized by an acid with a molecular weight of at least 100 g / mol. The acid can be a monomeric acid or a polymeric acid. If the acid is a polymeric acid, the molecular weight refers to the number-average molecular weight Mn. The number-average molecular weight can be suitably determined by gel permeation chromatography.

[0027] In a preferred embodiment, the acid has a molecular weight of at least 150 g / mol. Typically, the acid has a molecular weight of 2000 g / mol or lower, preferably 1500 g / mol or lower. In some embodiments, the molecular weight of the acid is 1000 g / mol or lower. Although acids can exist in polymeric form, they are generally unsuitable as film-forming binders.

[0028] The acidic group of an acid is typically selected from carboxylic acid groups, phosphorus-containing acidic groups, and sulfonic acid groups. Examples of phosphorus-containing acidic groups include phosphonic acid groups, as well as monoesters and diesters of phosphoric acid. In embodiments in which the acidic group contains phosphorus, the acid preferably has a molecular weight of 250 to 2000 g / mol.

[0029] The acid may contain 1, 2 or more acidic groups per molecule. Preferably, the molecule contains 1 or 2 acidic groups per molecule. The number of acidic groups per molecule can also be expressed as the average functionality, i.e., the number of acidic groups in the sample divided by the number of molecules in the sample. Preferably, the average functionality is in the range of 0.9 to 1.2 acidic groups per molecule.

[0030] Suitable examples of acids are fatty acids, such as those with 8 to 18 carbon atoms. Very good results have been obtained so far with sulfonic acids, especially aromatic sulfonic acids, such as p-toluenesulfonic acid.

[0031] When the acid is a polymeric acid, it suitably contains polyether segments or polyester segments.

[0032] Polymeric acids can be linear or branched polymers. Preferably, they are substantially linear polymers. Polymeric acids can be based on one or more types of monomers. In some embodiments, the polymeric acid contains ester groups. The polymeric acid can be a polyester, such as a polyester based on dicarboxylic acids, diols, and optionally monools, monocarboxylic acids, and combinations thereof. If a branched polyester is desired, it can include structural units for esterification having three or more esterification functional groups. Alternatively, polymers containing ester groups can be prepared by ring-opening polymerization of lactones. Suitable examples of lactones include ε-caprolactone and δ-valerolactone.

[0033] In other embodiments, the polymeric acid comprises an ether group. The polymeric acid can be a polyether, such as a polyether obtained by ring-opening polymerization of a cyclic ether group, for example, epoxides and oxetanes. Examples of suitable epoxides include ethylene oxide, propylene oxide, glycidyl ethers, glycidyl esters, and mixtures thereof. Suitable oxetanes include unsubstituted or substituted oxetanes, such as trimethylolpropaneoxetane. Polymerization of hydroxyl-functionalized cyclic ethers can yield branched polyether structures.

[0034] In other embodiments, the polymeric acid comprises ester groups and ether groups. In one embodiment, the polymeric acid may be a block copolymer comprising at least one polyether block and at least one polyester block. Alternatively, the ester groups and ether groups may be randomly distributed.

[0035] Acidic groups can be introduced into polymers using known methods.

[0036] Acidic phosphate esters are suitably prepared by reacting one phosphoric acid equivalent of an esterifying phosphorus compound with one to two equivalents of a hydroxyl-functionalized polymer.

[0037] If one equivalent of a monohydroxy functional polymer is used for each phosphoric acid equivalent of the esterifying phosphoric acid compound, a monoester is formed. If two equivalents are used, a diester is formed. If an amount between one and two equivalents is used, a mixture of monoesters and diesters is formed.

[0038] As used herein, the term "phosphorus compound for esterification" is understood to refer to those phosphorus compounds that can react with hydroxyl compounds to form phosphate esters, such as phosphorus oxychloride, phosphorus pentoxide, polyphosphates, and acetyl phosphates. For additional examples, see German patent application No. DE-A 2,726,854. Phosphorus pentoxide and polyphosphates are preferred.

[0039] The reaction of the phosphorus compound and the hydroxyl compound for esterification described above is preferably carried out in the absence of solvent at a temperature of up to about 100°C. However, this reaction can also be carried out in the presence of a suitable inert solvent, for example, see European patent application EP 0193019 A.

[0040] Polymers having carboxylic acid groups can be suitably prepared by reacting hydroxyl-functionalized, primary amine-functionalized, or secondary amine-functionalized polymers with cyclic carboxylic anhydrides. Suitable examples of cyclic carboxylic anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, succinic anhydride, and phthalic anhydride. Alternatively, the ring-opening polymerization of lactones can begin with a carboxylic acid to obtain carboxylic acid-functionalized polyesters.

[0041] Polymers with sulfonic acid groups can be prepared by treating alkyl polymers with sulfur dioxide and oxygen in the presence of a free radical forming agent, by oxidation of thiol functional polymers, or by treating halogenated functional polymers with sodium sulfate followed by acidification.

[0042] Typically, at least 5 mol% of the tertiary amine groups of the comb polymer are neutralized by an acid with a molecular weight of at least 100 g / mol. In a preferred embodiment, at least 10 mol% of the tertiary amine groups of the comb polymer are neutralized. Particularly preferably, 15 to 100 mol%, and most preferably 20 to 100 mol% of the tertiary amine groups are neutralized. In some embodiments, the amount of acid used to neutralize the tertiary amine groups may be higher than the theoretical amount used to neutralize 100 mol% of the tertiary amine groups. However, the amount of acid is typically in the range of 5 to 130% of the theoretical amount required to neutralize the tertiary amine groups.

[0043] Neutralization of the tertiary amine groups can suitably be achieved by combining the comb polymer with the acid and mixing the two components. The comb polymer or the acid, or both, can suitably be provided as a solution in one or more organic solvents, thereby reducing viscosity and facilitating processing and mixing. Neutralization and salt formation are thought to be facilitated by maintaining the composition at ambient temperature or elevated temperature for a specific period of time. In an exemplary embodiment, the composition is maintained at a temperature in the range of 20 to 80°C for 20 minutes to 24 hours after mixing to equilibrate the salt formation.

[0044] The comb-shaped polymers of the present invention typically have a low content of quaternary ammonium groups or contain no such groups at all. In a typical embodiment, all nitrogen atoms in the polymer are present as quaternary ammonium groups, ranging from 0.0 to 4.0 mol%, preferably from 0.0 to 0.5 mol%.

[0045] The comb-shaped polymers of the present invention can be suitably prepared from a base polymer having suitable functional groups connected to the side branches. In a preferred embodiment, the base polymer is a copolymer of styrene and maleic anhydride. Such copolymers can be prepared by known methods, such as free radical polymerization. Copolymers of styrene and maleic anhydride are also commercially available.

[0046] Branched groups a) can be attached to the styrene-maleic anhydride base copolymer by reacting it with a suitable modifier a).

[0047] In one embodiment, the modifier a) is a polyoxyalkylene monoamine, which is a C1-C4 alcohol-based polyether constructed from ethylene oxide and / or propylene oxide and carrying a primary amino group; the weight ratio between ethylene oxide units and propylene oxide units is typically 5:95 to 100:1, preferably 30:70 to 70:30. The number-average molecular weight of the polyoxyalkylene monoamine is typically 500 g / mol to 3000 g / mol.

[0048] In other embodiments, the modifier a) is a monohydroxyl-terminated polyether: these can be prepared, for example, by alkoxylation of a monofunctional alcohol with an olefin oxide, aliphatic or aromatic glycidyl ether, such as an alkanol, cycloalkanol, or phenol; the olefin oxide is such as ethylene oxide, propylene oxide, butene oxide, or styrene oxide; and the aliphatic or aromatic glycidyl ether is such as isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresol glycidyl ether, and phenyl glycidyl ether. Mixtures of these raw materials can also be used. In the case of mixed polyethers, they can be arranged in a statistical, gradient, or block configuration. These polyethers often have a number average molecular weight (Mn) of about 100 to 25,000. n The concentration is typically 150 to 15,000 g / mol, and more often 200 to 10,000 g / mol. Polyethers based on ethylene oxide, propylene oxide, or mixtures thereof are preferred.

[0049] Branched groups b) can be attached to the styrene-maleic anhydride base copolymer by reacting it with a suitable modifier b).

[0050] Examples of suitable modifiers (b) include polyamine compounds containing a primary amine group and at least one tertiary amine group. Suitable diamines include, for example, N,N-dialkylaminoalkylamines. A preferred diamine is N,N-dimethylaminopropylamine. Other available amines are diethylaminopropylamine (DEAPA), dimethylaminobutylamine (DMABA), dimethylaminoethylamine (DMAEA), aminopropylmorpholine, and diisopropylaminopropylamine (DIAPA).

[0051] As described above, the comb-shaped polymers of the present invention are well-suited for use as wetting agents and / or dispersants in colorants.

[0052] Therefore, the present invention also relates to a composition comprising:

[0053] (A) The comb-shaped polymer of the present invention,

[0054] (B) at least one colorant, and

[0055] (C) At least one diluent.

[0056] Suitable colorants include pigments, dyes, and fillers used to provide opacity, as well as combinations thereof.

[0057] Examples of suitable colorants can be found on page 9, line 30 to page 13, line 16 of international patent application PCT / EP2018 / 081346, and on page 6, line 32 to page 9, line 33 of JP 6248838 B. Additionally, Pigment Red-291, Pigment Yellow-231, Pigment Green-62, Pigment Green-63, Raven 5000 Ultra 2 (Birla Carbon product), Raven 5000 Ultra 3 (Birla Carbon product), COLOUR BLACK FW 100 (Orion Engineered Carbons product), COLOUR BLACK FW 171 (Orion Engineered Carbons product), COLOUR BLACK FW 200 (Orion Engineered Carbons product), COLOUR BLACK FW 255 (Orion Engineered Carbons product), COLOUR BLACK FW 310 (Orion Engineered Carbons product), Denka BLACK, and other carbon blacks, single-walled carbon nanotubes, or multi-walled carbon nanotubes for battery applications can be mentioned.

[0058] The composition also contains at least one diluent. Suitable diluents include water, organic liquids, and mixtures thereof. Examples of organic liquids include organic solvents, which are typically volatile liquids that reduce the viscosity of the composition. Examples of organic solvents include alkyl ketones, alkyl carboxylic acids, and alkyl esters of alkanols, especially liquids containing up to and including a total of 6 or 8 carbon atoms. Specific examples include dialkyl ketones and cycloalkyl ketones, such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyl isopentyl ketone, methyl n-pentyl ketone, and cyclohexanone; alkyl esters, such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, ethyl formate, methyl propionate, methoxypropyl acetate, and ethyl butyrate; glycols and glycol esters and ethers, such as ethylene glycol, 2-ethoxyethanol, 3-methoxypropylpropanol, 3-ethoxypropylpropanol, 2-butoxyethyl acetate, 3-methoxypropyl acetate, 3-ethoxypropyl acetate, and 2-ethoxyethyl acetate; alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol; and dialkyl ethers and cycloethers, such as diethyl ether and tetrahydrofuran.

[0059] In other embodiments, the solvent comprises an aliphatic group, an aromatic group, or a mixture thereof. Examples include non-halogenated aromatic hydrocarbons (e.g., toluene and xylene), halogenated aromatic hydrocarbons (e.g., chlorobenzene, dichlorobenzene, chlorotoluene), non-halogenated aliphatic hydrocarbons (e.g., straight-chain and branched aliphatic hydrocarbons containing 6 or more carbon atoms, which are fully and partially saturated), halogenated aliphatic hydrocarbons (e.g., dichloromethane, carbon tetrachloride, chloroform, trichloroethane), and natural nonpolar organic substances such as vegetable oils, sunflower oil, linseed oil, terpenes, and glycerides.

[0060] Other examples of organic liquids include so-called reactive diluents. Reactive diluents are organic liquids that have functional groups that can participate in chemical curing reactions. Examples of reactive diluents include glycidyl ethers and glycidyl esters having one or more epoxy groups, and acrylates or methacrylates having one or more (meth)acryloyl groups.

[0061] Other components may be included in the composition if desired. Examples of other components include film-forming binders, other resins and polymers, reactive diluents and solvents, curing catalysts, and other additives. The selection of other components depends on the intended use of the coloring composition. In exemplary embodiments, the coloring composition is formulated as an inkjet composition, as an automotive primer composition, or as a composition for color filters, particularly as a color filter for flat panel displays.

[0062] As coating compositions or ink compositions, they can be used in a wide range of applications, such as automotive coatings, architectural coatings, protective coatings (e.g., coatings for ships or bridges), can and roll coatings, wood and furniture coatings, industrial coatings, plastic coatings, wire enamels, food and seed coatings, or leather coatings (for natural and artificial leather). Coating materials include paste-like materials that typically have a high content of solids and a low content of liquid components, such as pigment pastes or effect pigment pastes (using pigments based on aluminum, silver, brass, zinc, copper, bronze (e.g., golden copper powder), or iron oxide-aluminum oxide); examples of effect pigments are interfering pigments and pearlescent pigments, such as metal oxide-mica pigments, bismuth oxychloride, or basic lead carbonate.

[0063] When formulating a coloring composition as a composition for use in a color filter, it is preferable to include an alkali-soluble resin in the composition. Examples of suitable alkali-soluble resins can be found on page 14, lines 20 to 15, line 21 of International Patent Application PCT / EP2018 / 081346, and on page 11, lines 20 to 13, line 6 of JP 6248838B.

[0064] The composition for color filters used in flat panel displays also preferably comprises an olefinically unsaturated component having one or more olefinically unsaturated groups. Examples of such components can be found on page 15, line 23 to page 16, line 33 of International Patent Application PCT / EP2018 / 081346.

[0065] Preferably, the composition further comprises a film-forming binder (D).

[0066] In this example, the film-forming adhesive can be any suitable organic polymer, depending on the intended use of the composition. The film-forming adhesive can be selected from any suitable thermoplastic polymer and any suitable crosslinkable polymer.

[0067] Examples of suitable thermoplastic polymers are poly(meth)acrylate, polyacrylonitrile, polystyrene, styrene-based plastics (e.g., ABS, SEBS, SBS), polyester, polyvinyl ester, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, thermoplastic polyurethane (TPU), polyvinyl chloride, polyoxymethylene, polyethylene, or polypropylene.

[0068] The crosslinkable film-forming adhesive as defined herein has at least one crosslinkable functional group. Any conventional crosslinkable functional group known to those skilled in the art is considered herein. More particularly suitable crosslinkable functional groups include hydroxyl, amino, carboxylic acid groups, unsaturated carbon double bonds, isocyanates, polyisocyanates, and epoxides, such as glycidyl ethers. The crosslinkable film-forming adhesive is crosslinkable or curable in an exothermic or endothermic manner. The crosslinkable film-forming adhesive is crosslinkable or curable in a temperature range of -20°C to 250°C. The crosslinkable film-forming adhesive is preferably selected from at least one of the following: epoxy resins; polyesters, wherein the polyester may be unsaturated; vinyl ester-based resins, poly(meth)acrylates, polyurethanes, polyureas, polyamides, polystyrene, polyethers, polycarbonates, polyisocyanates, and melamine-formaldehyde resins. Such film-forming adhesives and methods for their preparation are known to those skilled in the art.

[0069] The present invention also relates to the use of the comb-shaped polymer according to the invention as a wetting agent and / or dispersant for solid particles.

[0070] Preferably, the solid particles comprise at least one of pigments, dyes, and fillers, as described above.

[0071] The present invention also relates to a method for dispersing solid particles in a dispersion medium, wherein the dispersion medium includes the comb-shaped polymer of the present invention. The method typically involves mixing the solid particles, the comb-shaped polymer of the present invention, and the dispersion medium while applying a shear force. Example

[0072] raw material:

[0073] SMA 1000: Styrene-maleic anhydride copolymer (styrene / maleic anhydride molar ratio = 1 / 1)

[0074] (Polyscope)

[0075] SMA 2000: Styrene-maleic anhydride copolymer (styrene / maleic anhydride molar ratio = 2 / 1)

[0076] (Polyscope)

[0077] SMA 3000: Styrene-maleic anhydride copolymer (styrene / maleic anhydride molar ratio = 3 / 1)

[0078] (Polyscope)

[0079] Styrene: (Sigma-Aldrich)

[0080] Maleic anhydride: (Sigma-Aldrich)

[0081] α-MSD: α-methylstyrene dimer (Sigma-Aldrich)

[0082] AMBN: 2,2'-Azobis(2-methylbutyronitrile) (Sigma-Aldrich)

[0083] PMA: 1-Methoxy-2-propyl Acetate (DOW Chemicals)

[0084] PM: 1-Methoxy-2-Propyl Alcohol (DOW Chemicals)

[0085] Jeffamine M 2070: Amine-terminated EO / PO polyether (Huntsman)

[0086] Jeffamine M 2005: Amine-terminated EO / PO polyether (Huntsman)

[0087] DMAPA: N,N-Dimethylaminopropylamine (Huntsman)

[0088] BzCl: Benzyl chloride (Sigma-Aldrich)

[0089] BzBr: Benzyl bromide (Sigma-Aldrich)

[0090] Lutensol AO11: C13-C15 alkoxylated polyethylene glycol (number of ethylene oxide units: 11) (BASF)

[0091] MPEG-350: Methoxylated polyethylene glycol (number of ethylene oxide units: 8) (Sigma-Aldrich)

[0092] ε-caprolactone: (Sigma-Aldrich)

[0093] δ-Velolactone: (Sigma-Aldrich)

[0094] KOH: Potassium hydroxide (Sigma-Aldrich)

[0095] DBSA: Dodecylbenzenesulfonic acid (Sigma-Aldrich)

[0096] Phosmer M: (2-methacryloyloxy)ethyl phosphate (Uni-Chemical), theoretical molecular weight = 210.12 g / mol

[0097] MAA: Methacrylic acid (Sigma-Aldrich), theoretical molecular weight = 86.06 g / mol

[0098] PTSA: p-Toluenesulfonic acid, theoretical molecular weight = 172.12 g / mol

[0099] BA: Benzoic acid, theoretical molecular weight = 122.12 g / mol.

[0100] Gel permeation chromatography (GPC)

[0101] According to DIN 55672-1:2007-08, the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution were determined at 35 °C using a high-performance liquid chromatography (HPLC) pump (WATERS 600 HPLC pump) and a refractive index detector (WATERS 410). As separation columns, a combination of three Styragel columns from WATERS, with dimensions of 300 mm x 7.8 mm ID / column, a particle size of 5 μm, and pore sizes of HR4, HR2, and HR1, was used. The eluent was tetrahydrofuran containing 1% dibutylamine, and the elution rate was 1 mL / min. Routine calibration was performed using polystyrene standards.

[0102] Detection of nonvolatile matter content (solid content):

[0103] Accurately weigh the sample (1.0 ± 0.2 g of test substance) into a pre-dried aluminum pan and add approximately 2 mL of ethanol. After homogenization, dry it in a varnish drying oven at 150 °C for 20 minutes, cool it in a desiccator, and then weigh it again. The residue corresponds to the solids content in the sample (ISO 3251).

[0104] Amine value detection:

[0105] Accurately weigh 1.5 to 3.0 g of sample into an 80 mL beaker and dissolve in 50 mL of acetic acid. Using an automated titration apparatus equipped with a pH electrode, titrate the solution with 0.1 mol / L HClO4 acetic acid solution after neutralization. Use the inflection point of the pH titration curve as the titration endpoint and obtain the amine value using the following formula.

[0106] Amine value [mgKOH / g] = (561 × 0.1 × f × V) / (W × S)

[0107] (Where f is the coefficient of the titrant, V is the titration volume at the titration endpoint [mL], W is the weight of the sample [g], and S is the concentration of solids in the sample [wt%])

[0108] Acid value testing:

[0109] Accurately weigh 1.5 to 3.0 g of sample into an 80 mL beaker and dissolve in 50 mL of ethanol. Using an automated titration apparatus equipped with a pH electrode, neutralize and titrate the solution with 0.1 mol / L ethanol-KOH solution. Use the inflection point of the pH titration curve as the titration endpoint and obtain the amine value using the following formula.

[0110] Acid value [mgKOH / g] = (561 × 0.1 × f × V) / (W × S)

[0111] (Where f is the coefficient of the titrant, V is the titration volume at the titration endpoint [mL], W is the weight of the sample [g], and S is the concentration of solids in the sample [wt%])

[0112] Total acid value detection:

[0113] Accurately weigh 1.5 to 3.0 g of sample into an 80 mL beaker and dissolve it in 40 mL of pyridine and 10 mL of deionized water. The 80 mL beaker is fitted with a lid and heated at 70 °C in a temperature-controlled zone with stirring or in a water bath for 60 minutes. After cooling, the solution is titrated with a 0.1 mol / L NaOH aqueous solution using an automated titration apparatus equipped with a pH electrode. The inflection point of the pH titration curve is used as the titration endpoint, and the amine value is obtained using the following formula.

[0114] Total acid value [mgKOH / g] = (561 × 0.1 × f × V) / (W × S)

[0115] (Where f is the coefficient of the titrant, V is the titration volume at the titration endpoint [mL], W is the weight of the sample [g], and S is the concentration of solids in the sample [wt%])

[0116] Synthesis of styrene-maleic anhydride copolymer (I-SMA 1000 / I-SMA 1081)

[0117] 51.4 g of PMA was added to the reaction vessel and heated to 120 °C while stirring. Then, 18.3 g of maleic anhydride, 19.5 g of styrene, and 2.1 g of AMBN dissolved in 8.7 g of PMA were added dropwise to the reaction vessel. The reaction was carried out at 120 °C for 1 hour. After cooling, a styrene-maleic anhydride copolymer (I-SMA 1000) was obtained.

[0118] I-SMA 1000 has a solid content of 40% and a total acid value of 211 mg KOH / g.

[0119] Synthesis of styrene-maleic anhydride copolymer (I-SMA 2000)

[0120] 3.7 g of α-MSD and 37.9 g of PMA were added to the reaction vessel, and the mixture was heated to 130 °C while stirring. Then, 14.8 g of maleic anhydride, 26.9 g of styrene, and 2.1 g of AMBN dissolved in 14.6 g of PMA were added dropwise to the reaction vessel. The reaction was carried out at 130 °C for 1 hour. After cooling, a styrene-maleic anhydride copolymer (I-SMA 2000) was obtained.

[0121] I-SMA 2000 has a solid content of 47.5% and a total acid value of 150 mg KOH / g.

[0122] Synthesis of Amine Comb Copolymer C-1

[0123] 39.5 g of I-SMA 2000 was added to the reaction vessel, and the mixture was heated to 70 °C with stirring. Then, 35.5 g of Jeffamine M 2070 and 3.9 g of DMAPA were added dropwise to the reaction vessel. The reaction was carried out at 170 °C for 4 hours. PMA was distilled off during the reaction.

[0124] Synthesis of Amination Comb Copolymers C-2 to C-8

[0125] Amination comb copolymers C-2 to C-8 were synthesized using the same process as described for amination comb copolymer C-1, except that different types and amounts of branched monomers, pigment affinity groups, and additional solvents were used if necessary (details are shown in Table 1).

[0126] Synthesis of Amination-modified random copolymer RC-1

[0127] 85.0 g of PMA was added to the reaction vessel. Then, 52.8 g of SMA 1000 was added while stirring, and the mixture was heated to 70°C. Next, 7.2 g of DMAPA was added dropwise to the reaction vessel. The reaction was carried out at 170°C for 4 hours. PMA was distilled off during the reaction.

[0128] Synthesis of quaternized comb copolymer QC-1

[0129] 38.5 g of comb copolymer C-1, 58.6 g of PMA, and 2.9 g of benzyl chloride were added to a reaction vessel, and the vessel was heated to 120 °C. The quaternization reaction was carried out at 120 °C for 4 hours. Subsequently, quaternized comb copolymer QC-1 was obtained.

[0130] The quaternized comb copolymer QC-1 has a solid content of 40% and an amine value of 4 mg KOH / g.

[0131] Synthesis of Quaternized Comb Copolymers QC-2 to QC-4

[0132] Quaternized comb copolymers QC-2 to QC-6 were synthesized according to the same procedure as described for quaternized comb copolymer QC-1, except that different types and amounts of quaternizing agents and solvents were used (details are shown in Table 2).

[0133] Preparation of waterborne comb copolymer WC-1

[0134] 50.0 g of comb copolymer C-1 and 50.0 g of deionized water were added to a reaction vessel, and the vessel was heated to 100 °C with stirring. Distillation of PMA and deionized water from the mixture was carried out at 100 °C under reduced pressure for 6 hours. After cooling to 60 °C, 50.0 g of deionized water was added to the reaction vessel, and distillation was performed multiple times. After adding an appropriate amount of deionized water to adjust the solid content, the aqueous comb copolymer WC-1 was obtained.

[0135] The aqueous comb copolymer WC-1 has a solid content of 40% and an amine value of 36 mg KOH / g.

[0136] Synthesis of acid polymer AP-1

[0137] 0.3 g of KOH, 77.5 g of MPEG-350, and 22.2 g of succinic anhydride were added to the reaction vessel, and the vessel was heated to 80 °C. The synthesis of the acidic polymer AP-1 was carried out at 80 °C for 1 hour.

[0138] The acidic polymer AP-1 has a solid content of 100%, an acid value of 124 mg KOH / g, and a theoretical molecular weight of 450 g / mol.

[0139] Synthesis of acid polymer AP-2

[0140] 86.0 g of Lutensol AO11 and 14.0 g of PAA were added to the reaction vessel, and the reaction vessel was heated to 80 °C. The synthesis of the acid polymer AP-2 was carried out at 80 °C for 1 hour.

[0141] The acidic polymer AP-2 has a solid content of 100%, an acid value of 186 mg KOH / g, and a theoretical molecular weight of 772 g / mol.

[0142] Synthesis of acid polymer AP-3

[0143] 0.3 g of KOH, 77.9 g of MPEG-350, and 21.8 g of maleic anhydride were added to the reaction vessel, and the reaction vessel was heated to 80 °C. The synthesis of the acidic polymer AP-3 was carried out at 80 °C for 1 hour.

[0144] The acid polymer AP-1 has a solid content of 100%, an acid value of 125 mg KOH / g, and a theoretical molecular weight of 448 g / mol.

[0145] Synthesis of acid polymer AP-4

[0146] 0.1 g of DBSA, 43.7 g of MPEG-350, 27.4 g of ε-caprolactone, and 16.1 g of δ-valerolactone were added to the reaction vessel, and the vessel was heated to 80 °C. The reaction was carried out at 80 °C for 1 hour. Subsequently, 12.4 g of succinic anhydride and 0.3 g of KOH were added to the reaction vessel. The synthesis of the acidic polymer AP-4 was carried out at 80 °C for 1 hour.

[0147] The acidic polymer AP-4 has a solid content of 100%, an acid value of 70 mg KOH / g, and a theoretical molecular weight of 780 g / mol.

[0148] Synthesis of acid polymer AP-5

[0149] 0.1 g of DBSA, 44.9 g of MPEG-350, 28.2 g of ε-caprolactone, and 16.5 g of δ-valerolactone were added to the reaction vessel, and the vessel was heated to 80 °C. The reaction was carried out at 80 °C for 1 hour. Subsequently, 10.3 g of PPA was added to the reaction vessel. The synthesis of the acidic polymer AP-5 was carried out at 80 °C for 1 hour.

[0150] The acidic polymer AP-5 has a solid content of 100%, an acid value of 137 mg KOH / g, and a theoretical molecular weight of 875 g / mol.

[0151] Synthesis of neutralization product S-1

[0152] 30.9 g of the amination comb copolymer C-1, 9.2 g of the acid polymer AP-1, and 59.9 g of PMA were placed in a reaction vessel, and the reaction vessel was heated to 80 °C. The neutralization reaction was carried out at 80 °C for 1 hour. The experimental results of the neutralization product S-1 are shown in Table 4.

[0153] Synthesis of neutralization products S-2 to S-24

[0154] Neutralized products S-2 to S-24 were synthesized using the same process as described for neutralized product S-1, except that different types of amination comb copolymers, acid polymers and components, different molar ratios of amines to acids, and different amounts of solvent and deionized water were used (details are shown in Table 4).

[0155] Synthesis of Alkali-Soluble Resin B1

[0156] 300 g of PMA was placed in a reaction vessel. 137 g of BzMA, 34 g of methacrylic acid, and 1.65 g of AMBN were added metered over 180 minutes at 120 °C. After the metered addition, the subsequent reaction time was 120 minutes. The solids content was then adjusted to 35% by weight with PMA (DIN EN ISO 3251:2008-06, at 150 °C for 20 minutes). The number-average molecular weight was 7875 g / mol.

[0157] Table 1 Formulations of amination comb copolymers C-1 to C-8 and amination random copolymer RC-1

[0158]

[0159] Table 2 Formulations of quaternized comb copolymers QC-1 to QC-4

[0160]

[0161] Table 3 Formulations of acidic copolymers AP-1 to AP-5

[0162]

[0163] Table 4 shows the formulations of neutralization products S-1 to S-24.

[0164]

[0165] Preparation of coloring composition:

[0166] Preparation of red, green and blue dispersions for color filter applications :

[0167] PG-58: Fastogen Green A110 (DIC)

[0168] PR-254: Irgaphor Red (red) BT-CF (BASF)

[0169] PB-15:6: Fastogen Blue EP-193 (DIC)

[0170] A general process for preparing dispersion R-1 for color filter applications:

[0171] 4.3 g of alkali-soluble resin B1 and 9.4 g of dispersant S-1, as shown in Table 4, were placed in a 140 ml glass bottle. Subsequently, 28.8 g of PMA was added to the glass bottle to dissolve the alkali-soluble resin R1 and the dispersant. Then, 7.5 g of PR-254 and 150 g of zirconia beads (diameter: 0.4-0.6 mm) were added to the glass bottle. This dispersion process was carried out at 30°C for 5 hours in a LAU-Disperser DAS200. After 5 hours, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0172] A common process for preparing dispersions R-2 to R-5, G-1 to G8, and B-1 to B-4 for color filter applications:

[0173] Dispersions R-2 to R6, G-1 to G-9 and B-1 to B-5 are prepared according to the process described for dispersion R-1 (details are shown in Table 5).

[0174] Table 5 Formulations of red, green, and blue dispersions for color filter applications.

[0175]

[0176] Production of resist inks

[0177] BYK-330: Organosilicon additive (BYK-Chemie)

[0178] Aronix M305: Pentaerythritol Triacrylate (TOA GOSEI)

[0179] Omnirad 369: Formerly known as Irgacure 369, 2-benzyl-2-(dimethylamino)-4'-morpholinopropylphenyl ketone (I GM Resins BV)

[0180] The formulation of the resist ink is as follows:

[0181]

[0182] Application test results

[0183] Viscosities of red, green, and blue dispersions:

[0184] The viscosity of the red, green, and blue dispersions was determined using the BROOKFIELDVISCOMETER DV-II+ (BROOKFIELD, upper viscosity limit: 1000 mPa·s).

[0185] Particle sizes of red, green, and blue dispersions:

[0186] The particle size (median diameter: D50) of the red, green, and blue dispersions was determined using an ELSZ-1000 particle size analyzer (Otsuka Electronics).

[0187] Colorimetric properties:

[0188] Red, green, and blue resist inks were applied to a glass plate using a doctor blade coater No. 4 (wet film thickness 9.16 μm), and the coating was dried at 80°C for 3 minutes. The dried coating was then gradually immersed in a 0.05% KOH aqueous solution (interval: 10–60 seconds). After washing with water, the coating was wiped with KimWipes (a product of Kimberly Clark Corporation), and its appearance was marked as described below:

[0189] 1 (Excellent): Completely removes coating after wiping.

[0190] 2 (Excellent): Partially remove the coating after wiping.

[0191] 3 (Good): The coating was not completely removed, but most of the surface area of ​​the coating was removed after wiping.

[0192] 4 (Poor): The coating was not removed, but the surface of the coating was partially removed after wiping.

[0193] 5 (Bad): The appearance of the coating remains unchanged after wiping.

[0194] Resolubility in PMA

[0195] Red, green, and blue resist inks were applied to a glass plate using a doctor blade coater No. 4 (wet film thickness 9.16 μm). The coating was dried at 80°C for 3 minutes. One drop of PMA was placed on the coating and immediately wiped with KimWipes. The appearance of the coating after wiping is shown in the markings below:

[0196] 1 (Excellent): Completely removes coatings from trace PMA droplets after wiping.

[0197] 2 (Excellent): Partially removes the coating in trace PMA droplets after wiping.

[0198] 3 (Good): No coating was removed from trace amounts of PMA, but most of the coating surface was removed after wiping.

[0199] 4 (Poor): The coating in trace amounts of PMA was not removed, but the surface of the coating was partially removed after wiping.

[0200] 5 (Bad): The appearance of the coating remains unchanged after wiping.

[0201] Examples 1-10: Viscosity and particle size of red (R), green (G), and blue (B) dispersions, and color development properties and resolubility of red (R), green (G), and blue (B) resist inks in PMA.

[0202] The viscosity (mPa·s, at 20°C, rotation: 60 rpm) and particle size (D50) of the red, green and blue dispersions, as well as the color development properties and resolubility of the red, green and blue resist inks in PMA are shown in Table 6.

[0203] Table 6 shows the viscosity and particle size of the red, green, and blue dispersions, as well as the color development properties and resolubility of the red, green, and blue resist inks in PMA.

[0204]

[0205] Comparative Examples C-1 to C-7: Viscosity and particle size of red (R), green (G), and blue (B) dispersions, as well as color development properties and resolubility of red, green, and blue resist inks in PMA.

[0206] The viscosity (mPa·s, at 20°C, rotation: 60 rpm) and particle size (D50) of the red, green and blue dispersions are shown in Table 8, and the color development properties and resolubility of the red, green and blue resist inks in PMA are shown in Table 7.

[0207] Table 7 shows the viscosity and particle size of the red, green, and blue dispersions, as well as the color development properties and resolubility of the red, green, and blue resist inks in PMA.

[0208]

[0209] Based on the results shown in Tables 6 and 7, the red, green, and blue dispersions containing the neutralization product between the amination comb copolymer and the acid polymer exhibit excellent dispersibility and storage stability (Examples 1-10). Furthermore, the red, green, and blue resist inks containing these dispersions also exhibit excellent color development properties and resolubility in PMA.

[0210] However, the green dispersions (comparative examples C-3 and C-4) containing neutralization products between the amination comb copolymer and the acid polymer and low molecular weight acid components exhibit poor storage stability, and their resist inks exhibit poor color development properties and resolubility in PMA.

[0211] The red dispersion (Comparative Example C-1) containing the neutralization product between an amination (non-comb) copolymer and an acidic polymer or a low molecular weight acidic component showed poor dispersibility.

[0212] The green dispersion containing the amination comb copolymer (Comparative Example C-6) and the quaternization comb copolymer (Comparative Example C-5) showed poor dispersibility.

[0213] Red and blue dispersions containing quaternized comb copolymers (comparative examples C-2 and C-7) exhibit good dispersibility and storage stability, but their resist inks show poor resolubility in PMA.

[0214] Preparation of carbon black dispersions for solvent-based spray coatings:

[0215] Raven U3: Raven 5000Ultra 3 (Birla Carbons)

[0216] PMA: 1-Methoxy-2-propyl Acetate (DOW Chemicals)

[0217] General process for preparing solvent-based carbon black dispersion Bk-1:

[0218] 9.7 g of dispersant S-1 was placed in a 140 ml glass vial. Then, 36.0 g of PMA was added to the vial to dissolve the dispersant in the PMA. Next, 4.3 g of Raven 5000 Ultra 3 (Raven U3) and 150 g of zirconia beads (0.4-0.6 mm in diameter) were added to the vial. The dispersion process was carried out for 10 hours at 30°C in a LAU-Disperser DAS200. After 10 hours, the concentrate was filtered into a 50 ml glass vial to remove the zirconia beads.

[0219] General process for preparing solvent-based carbon black dispersions Bk-2 to Bk-6:

[0220] Solvent-based dispersions Bk-2 to Bk-6 were prepared according to the procedures described for dispersion Bk-1 (details are shown in Table 8).

[0221] Table 8 Formulations of solvent-based carbon black dispersions Bk-1 to Bk-6

[0222]

[0223] Examples 11-13: Viscosity and particle size of solvent-based carbon black dispersions Bk-1, Bk-3 and Bk-4

[0224] The viscosity (mPa·s, at 20°C, rotation: 60 rpm) and particle size (D50) of solvent-based carbon black dispersions Bk-1, Bk-2 and Bk-4 are shown in Table 9.

[0225] Table 9. Viscosities and particle sizes of solvent-based carbon black dispersions Bk-1, Bk-3, and Bk-4

[0226]

[0227] Comparative Examples 8-10: Viscosity and Particle Size of Solvent-Based Carbon Black Dispersions Bk-2, Bk-5, and Bk-6

[0228] The viscosity (mPa·s at 20°C, rotation: 60 rpm) and particle size (D50) of solvent-based carbon black dispersions Bk-2, Bk-5 and Bk-6 are shown in Table 10.

[0229] Table 10 Viscosities and particle sizes of solvent-based carbon black dispersions Bk-2, Bk-5, and Bk-6

[0230]

[0231] Based on the results shown in Tables 9 and 10, solvent-based black dispersions containing the neutralization product between the amination comb copolymer and the acid polymer show promising results as solvent-based carbon black dispersions for use in coatings for transportation vehicles (Examples 11-13).

[0232] On the other hand, the black dispersion containing the neutralization product between the aminated comb copolymer and the low molecular weight acidic component (Comparative Example C-8) and the black dispersion containing the quaternized comb copolymer (Comparative Example C-9) exhibited poor storage stability. Furthermore, the black dispersion containing the aminated comb copolymer (Comparative Example C-10) exhibited poor dispersibility.

[0233] Preparation of blue dispersions for water-based blue coatings:

[0234] G314: Sanyo Color (G-314)

[0235] BYK-011: Polymer-based defoamer (BYK-Chemie)

[0236] DYN 800N: BYK-DYNWET 800N, wetting agent (BYK-Chemie)

[0237] General process for preparing aqueous blue dispersion Bl-1:

[0238] 31.4 g of deionized water, 0.3 g of BYK-011, and 0.80 g of BYK-DYNWET800N were placed in a 140 ml glass bottle. Then, 7.50 g of dispersant S-15 was added to the glass bottle to dissolve it in the deionized water. Next, 10.00 g of Cyanine Blue G-314 and 150 g of zirconia beads (diameter: 0.4-0.6 mm) were added to the glass bottle. This dispersion process was carried out at 30°C for 8 hours in a LAU-Disperser DAS200. After grinding, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0239] General process for preparing aqueous blue dispersions Bl-2 to Bl-4:

[0240] Aqueous blue dispersions Bl-2 to Bl-4 are prepared according to the process described for dispersion Bl-1 (details are shown in Table 11).

[0241] Table 11 Formulations of aqueous blue dispersions Bl-1 to Bl-4

[0242]

[0243] Examples 14-15: Viscosity and particle size of aqueous blue dispersions Bl-1 to Bl-2

[0244] The viscosity (mPa·s, at 20°C, rotation: 60 rpm) and particle size (D50) of the aqueous blue dispersions Bl-1 to Bl-2 are shown in Table 12.

[0245] Table 12 Viscosity and particle size of aqueous blue dispersions Bl-1 to Bl-2

[0246]

[0247] Comparative Examples 11-12: Viscosity and Particle Size of Aqueous Blue Dispersions Bl-3 to Bl-4

[0248] The viscosity (mPa·s at 20°C, rotation: 60 rpm) and particle size (D50) of the aqueous blue dispersions Bl-3 to Bl-4 are shown in Table 13.

[0249] Table 13 Viscosity and particle size of aqueous blue dispersions Bl-3 to Bl-4

[0250]

[0251] Based on the results shown in Tables 12 and 13, the aqueous blue dispersion containing the neutralization product between the amination comb copolymer and the acid polymer shows promising results as an aqueous blue dispersion for use in coatings for transport vehicles (Examples 14-15).

[0252] On the other hand, the blue dispersion (Comparative Example C-11) containing the neutralization product between the aminated comb copolymer and the low molecular weight acidic component exhibited poor storage stability. Additionally, the blue dispersion (Comparative Example C-12) containing the aminated comb copolymer exhibited poor dispersibility.

[0253] Preparation of black dispersions for battery applications:

[0254] Denka Black: Denka carbon black (granular) (Denka)

[0255] BYK-017: Polymer-based defoamer (BYK-Chemie)

[0256] General process for preparing aqueous black dispersion WBk-1:

[0257] 15.2 g of deionized water and 0.1 g of BYK-017 were placed in a 70 ml glass bottle. Then, 0.70 g of dispersant S-15 was added to the glass bottle to dissolve it in the deionized water. Next, 4.0 g of Denka Black and 60 g of zirconia beads (diameter: 2.0 mm) were added to the glass bottle. This dispersion process was carried out at 30°C for 3 hours in a LAU-Disperser DAS200. After grinding, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0258] General process for preparing aqueous black dispersions WBk-2 to WBk-4:

[0259] Aqueous black dispersions WBk-2 to WBk-4 were prepared according to the process described for dispersion WBk-1 (details are shown in Table 14).

[0260] Table 14 Formulations of aqueous black dispersions WBk-2 to WBk-4

[0261]

[0262] Examples 16-17: Viscosity and particle size of aqueous black dispersions WBk-1 to WBk-2

[0263] The viscosity (mPa·s, at 20°C, rotation: 60 rpm and 6 rpm) and particle size (D50) of the aqueous black dispersions WBk-1 to WBk-2 are shown in Table 15.

[0264] Table 15 Viscosity and Particle Size of Aqueous Black Dispersions WBk-1 to WBk-2

[0265]

[0266] Comparative Examples 13-14: Viscosity and Particle Size of Aqueous Black Dispersions WBk-3 to WBk-4

[0267] The viscosity (mPa·s at 20°C, rotation: 60 rpm and 6 rpm) and particle size (D50) of the aqueous black dispersions WBk-3 to WBk-4 are shown in Table 16.

[0268] Table 16 Viscosity and Particle Size of Aqueous Black Dispersions WBk-3 to WBk-4

[0269]

[0270] Based on the results shown in Tables 15 and 16, the aqueous black dispersion containing the neutralization product between the amination comb copolymer and the acid polymer shows promising results as an aqueous black dispersion for use in lithium-ion batteries (Examples 16-17).

[0271] On the other hand, the black dispersion containing the neutralization product between the aminated comb copolymer and the low molecular weight acidic component (Comparative Example C-13) exhibits thixotropic behavior. Additionally, the black dispersion containing the aminated comb copolymer (Comparative Example C-14) exhibits poor dispersibility and high viscosity.

[0272] Preparation of blue dispersions for solvent-based blue coatings:

[0273] Heliogen Blue L7110F β-phthalocyanine blue organic pigment (BASF)

[0274] ethanol

[0275] Ethyl acetate.

[0276] General procedures for preparing solvent-based blue dispersion SB-1:

[0277] 29.4 g of a 9:1 mixture of ethanol and ethyl acetate was placed in a 100 ml glass vial, and 5.6 g of dispersant S-17 was added. Then, 15.0 g of Heliogen Blue L7110F and 50 g of zirconia beads (1.0-1.3 mm in diameter) were added to the vial. The dispersion process was carried out for 60 minutes in a LAU-Disperser DAS200.

[0278] General process for preparing solvent-based blue dispersions SB-2 to SB-11:

[0279] Solvent-based blue dispersions SB-2 to SB-11 were prepared according to the procedure described for dispersion SB-1 (details are shown in Table 17).

[0280] Table 17 Formulations of solvent-based blue dispersions SB-2 to SB-11

[0281]

[0282] Examples 18-24: Viscosity and particle size of solvent-based blue dispersions SB-1 to SB-7

[0283] The viscosities of the solvent-based blue dispersions SB-1 to SB-7 are shown in Table 18.

[0284] Table 18 Viscosity and Particle Size of Solvent-Based Blue Dispersions SB-1 to SB-7

[0285]

[0286] Comparative Examples 15-18: Viscosity and Particle Size of Solvent-Based Blue Dispersions SB-8 to SB-11

[0287] The viscosity and particle size of the solvent-based blue dispersions SB-8 to SB-11 are shown in Table 19.

[0288] Table 19 Viscosity and Particle Size of Aqueous Blue Dispersions SB-8 to SB-11

[0289]

[0290] Based on the results shown in Tables 18 and 19, solvent-based blue dispersions containing the neutralization product between the amination comb copolymer and the acid polymer show promising results as solvent-based blue dispersions for use in printing inks (Examples 18-25).

[0291] On the other hand, the blue dispersion (Comparative Example C-15) containing the neutralization product between the aminated comb copolymer and the low molecular weight acidic component exhibits a higher viscosity. Additionally, the blue dispersions (Comparative Examples C-16 to C-18) containing the aminated comb copolymer exhibit poor dispersibility.

Claims

1. A comb-shaped polymer having a polymer backbone and side branches connected to the polymer backbone, wherein the polymer backbone comprises polymeric units of vinyl aromatic monomers, and wherein the side branches comprise: a) Alkyl ether-terminated polyoxyethylene branches, and b) A tertiary amine functional branch, wherein the tertiary amine group is at least partially neutralized by an acid with a molecular weight of 100 g / mol to 2000 g / mol, wherein, if the acid is a polymeric acid, the acid comprises polyether segments or polyester segments, and the molecular weight relates to the number-average molecular weight Mn determined by gel permeation chromatography using a polystyrene standard. Furthermore, the side branches a) and b) are distributed in a random manner.

2. The comb-shaped polymer according to claim 1, wherein the acid has a molecular weight of 150 to 2000 g / mol, wherein, in the case that the acid is a polymeric acid, the molecular weight relates to the number average molecular weight Mn.

3. The comb-shaped polymer according to claim 1 or 2, wherein the acid comprises an acidic group, and the acidic group comprises at least one selected from carboxylic acid groups, phosphate groups, and sulfonic acid groups.

4. The comb-shaped polymer according to any one of the preceding claims, wherein at least 5 mol% of the tertiary amine groups are neutralized by an acid with a molecular weight of 100 g / mol to 2000 g / mol, wherein, if the acid is a polymeric acid, the acid comprises polyether segments or polyester segments, and the molecular weight relates to the number-average molecular weight Mn determined by gel permeation chromatography using a polystyrene standard.

5. The comb-shaped polymer according to any one of the preceding claims, wherein the alkyl ether-terminated polyoxyethylene side chain is connected to the polymer backbone via an imide group.

6. The comb-shaped polymer according to any one of the preceding claims, wherein the amine functional side chains are connected to the polymer backbone via imide groups.

7. The comb-shaped polymer according to any one of the preceding claims, wherein the polymer backbone comprises N-substituted maleimide polymeric units.

8. The comb-shaped polymer according to any one of the preceding claims, wherein the amine value of the polymer is in the range of 5 to 150 mg KOH / g.

9. A composition comprising: (A) The comb-shaped polymer according to any one of the preceding claims (B) at least one colorant, and (C) At least one diluent.

10. The composition of claim 9, wherein the composition further comprises a film-forming binder (D).

11. Use of the comb polymer according to any one of claims 1-8 as a wetting agent and / or dispersant for solid particles.

12. The use according to claim 11, wherein the solid particles comprise at least one of pigments, dyes, and fillers.

13. A method for dispersing solid particles in a liquid dispersion medium, wherein the comb-shaped polymer according to any one of claims 1-8 is present in the dispersion medium.

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