Comonomer having a salt functional group

Abstract

The present invention relates to comb polymers having a polymer backbone and lateral side chains attached to the polymer backbone, the lateral side chains comprising: (a) alkyl ether terminated polyalkylene oxide side chains; and (b) tertiary amine functional side chains, the tertiary amine groups being at least partially neutralized with an acid having a molecular weight in the range of 100 g / mol to 2000 g / mol, the molecular weight being related to the number average molecular weight Mn for the polymeric acid, wherein the lateral side chains (a) and (b) are distributed in a random order.

Description

Technical Field

[0001] The present invention relates to a comb polymer having an alkyl ether-terminated polyalkylene oxide side chain and a neutralized tertiary amine functional side chain, to a composition containing the comb polymer and at least one colorant, and to the use of the comb polymer as a wetting agent and / or dispersant for solid particles.

Background Art

[0002] US7078464 describes a composition containing an unsaturated carboxylate of an amine-functional styrene maleic anhydride copolymer. Its use as a pigment dispersant is also described. Preferred unsaturated carboxylic acids are acrylic acid and methacrylic acid.

[0003] WO2008 / 080580 describes a modified comb copolymer prepared by the reaction of an SMA resin with a polyalkylene oxide monoamine and a primary tertiary diamine. The tertiary amine groups are at least partially converted to quaternary ammonium salts. The modified comb copolymer is suitable as a pigment dispersion resin.

[0004] WO2013 / 189568 describes copolymers and their use as wetting agents and dispersants. These copolymers are prepared by reacting a main chain polymer with a primary amine or alcohol, each having at least one tertiary amine group, and then quaternizing. In some embodiments, the main chain polymer may be modified with a polyalkylene oxide monoamine.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Currently, there are requirements for polymers suitable for use as wetting agents and dispersants, which provide improved properties to pigment dispersions in aqueous media and organic solvent systems. In particular, there is a need for pigment dispersions with low viscosity, good storage stability, and broad compatibility with different types of binders used in coating compositions and other pigment-containing compositions. Pigment dispersions for the manufacture of color resists for flat panel displays need to provide improved development properties and good redissolvability. The polymer needs to be easily prepared from readily available raw materials and preferably can be easily prepared without the use of elaborate polymerization techniques.

Means for Solving the Problems

[0006] The present invention provides a comb polymer having a polymer backbone and lateral side chains linked to the polymer backbone, and these lateral side chains are (a) alkyl ether-terminated polyalkylene oxide side chains, and (b) tertiary amine-functional side chains, wherein the tertiary amine groups are at least partially neutralized by an acid having a molecular weight in the range of 100 g / mol to 2000 g / mol, and this molecular weight is related to the number average molecular weight Mn in the case of a polymeric acid, the tertiary amine-functional side chains, including The lateral side chains (a) and (b) are distributed in a random order.

[0007] The comb polymer of the present invention is suitable for use as a wetting agent and a dispersant, and provides improved properties to pigment dispersions in aqueous media and organic solvent systems. The comb polymer results in a pigment dispersion having low viscosity, good storage stability, and broad compatibility with different types of binders used in coating compositions and other pigment compositions. When used for pigment dispersions for the manufacture of color resists for flat panel displays, improved development properties and good redissolvability are observed. This polymer is easily prepared from readily available raw materials without the need to use elaborate polymerization techniques.

[0008] The polymer of the present invention includes a polymer backbone. The polymer backbone is a linear polymer or a branched polymer having repeating units. Preferably, the polymer backbone has a substantially or entirely linear structure. Generally, the type of polymer forming the polymer backbone is not particularly limited and may 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 ethylenically unsaturated monomers. Considering the wide variety of available ethylenically unsaturated monomers having additional functional groups, polymers and copolymers of such monomers (collectively referred to as (co)polymers) are preferred as the polymer backbone. Examples of suitable ethylenically 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.

[0009] In a preferred embodiment, the polymer backbone includes polymerized units (polymerization units) of vinyl aromatic hydrocarbon monomers, particularly including styrene.

[0010] More preferably, the polymer backbone includes polymerization units of N-substituted maleimide (N-substituted maleic imide). Particularly preferably, the lateral side chains (a) and (b) are linked to the polymer via the nitrogen atom of the polymerization unit of N-substituted maleimide.

[0011] In the polymer of the present invention, the lateral side chains are linked to the polymer backbone. Generally, the lateral side chains are covalently bonded to the polymer backbone. The resulting structure may also be referred to as a comb polymer.

[0012] Typically, two or more lateral side chains are covalently bonded to the polymer backbone.

[0013] The side chain contains an alkyl ether-terminated polyalkylene oxide side chain.

[0014] This alkyl ether generally has an alkyl group containing 1 to 32 carbon atoms. The alkyl group may be linear or branched. The alkyl group may similarly contain a cyclic group. In a preferred embodiment, the alkyl group has 1 to 8 carbon atoms.

[0015] This polyalkylene oxide group generally has a number average molecular weight in the range of 88 to 5000 g / mol. In a preferred embodiment, it is 132 to 4000 g / mol, more preferably 132 to 2000 g / mol. The number average molecular weight can be determined by gel permeation chromatography.

[0016] This polyalkylene oxide group contains polymerized units (polymerization units) of alkylene oxide. The alkylene oxide is preferably selected from ethylene oxide, propylene oxide, and combinations thereof. Particularly preferably, the polyalkylene oxide group contains polymerized units (polymerization) of ethylene oxide or consists of polymerized units of ethylene oxide. When the polyalkylene oxide side chain has polymerized units of more than one type of alkylene oxide, such units may be arranged statistically, in a gradient, or in blocks. The number of polymerized alkylene oxide units in the polyalkylene oxide side chain generally ranges from 1 to 114, for example, 3 to 91, or 4 to 45.

[0017] In one embodiment, the individual side chains have the same type of alkyl ether-terminated polyalkylene oxide group. In other embodiments, there may be multiple side chains having different types of such groups.

[0018] The side chains containing alkyl ether-terminated polyalkylene groups are generally linked to the polymer backbone via a linking group (linker group). Examples of suitable linking groups are ester groups, amide groups, and imide groups. In a preferred embodiment, the alkyl ether-terminated polyalkylene oxide side chains are linked to the polymer backbone via an imide group.

[0019] The comb polymers of the present invention further have tertiary amine-functional side chains. These tertiary amine-functional side chains contain a tertiary amine group. Generally, these side chains contain one tertiary amine group per side chain. The tertiary amine group has a linear, branched, or cyclic alkyl group linked to the amine nitrogen. In a typical embodiment, the alkyl group has 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms per alkyl group. In some embodiments, the alkyl group may form a cyclic structure having an amine nitrogen.

[0020] The side chains having a tertiary amine group are generally linked to the polymer backbone via a linking group (linker group). Examples of suitable linking groups are ester groups, amide groups, and imide groups. In a preferred embodiment, the tertiary amine-functional side chains are linked to the polymer backbone via an imide group.

[0021] The amount of the tertiary amine group in the comb polymers of the present invention is generally selected such that the comb polymer has 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 polymer is at most 120 mg KOH / g, more preferably at most 100 mg KOH / g. The amine value is related to the non-volatile content of the comb polymer. In a highly preferred embodiment, the amine value of the comb polymer is in the range of 15 to 100 mg KOH / g.

[0022] The lateral side chains (a) having an alkyl ether-terminated polyalkylene group and the lateral side chains (b) having a tertiary amine group are distributed in a random order. What this means is that these lateral side chains (a) and (b) are positioned along the polymer backbone without a specific order or structure, which is in contrast to a block copolymer, in which case a specific structure is present in a distinguishable part of the copolymer and not in other parts.

[0023] In the comb polymers of the present invention, the tertiary amine groups are at least partially neutralized by an acid having a molecular weight of at least 100 g / mol. The acid may be a monomeric acid or a polymeric acid. When the acid is polymeric, the molecular weight relates to the number average molecular weight Mn. The number average molecular weight can be appropriately determined by gel permeation chromatography.

[0024] In a preferred embodiment, the acid has a molecular weight of at least 150 g / mol. Generally, the acid has a molecular weight of 2000 g / mol or less, preferably 1500 g / mol or less. In some embodiments, the molecular weight of the acid is 1000 g / mol or less. The acid may be present in polymeric form, but generally is not suitable as a film-forming binder. The acidic groups of the acid are generally selected from carboxylic acid groups, phosphorus-containing acidic groups, and sulfonic acid groups. Examples of phosphorus-containing acid groups include phosphonic acid groups and mono- and diesters of phosphoric acid. In embodiments where the acidic group contains phosphorus, the acid preferably has a molecular weight in the range of 250 - 2000 g / mol.

[0025] 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 an average functionality, i.e., the number of acid groups in the sample divided by the number of molecules in the sample. Preferably, this average functionality is in the range of 0.9 - 1.2 acidic groups per molecule.

[0026] Examples of suitable acids are fatty acids, for example, fatty acids having 8 to 18 carbon atoms. At present, very good results have also been obtained with sulfonic acids, especially with aromatic sulfonic acids, for example, para-toluenesulfonic acid.

[0027] When the acid is a polymeric acid, it suitably has a polyether moiety or a polyester moiety.

[0028] The polymeric acid may be a linear polymer or a branched polymer. Preferably, it is an essentially linear polymer. The polymeric acid may be based on one or more types of monomers. In some embodiments, the polymeric acid has ester groups. The polymeric acid may be a polyester, for example, a polyester based on dicarboxylic acids, diols, and optionally monoalcohols, monocarboxylic acids, and combinations thereof. If a branched polyester is desired, it may include ester-forming building blocks having three or more ester-forming functional groups. Alternatively, a polymer containing ester groups may be prepared by ring-opening polymerization of lactones. Examples of suitable lactones include epsilon-caprolactone and delta-valerolactone.

[0029] In a further embodiment, the polymeric acid contains ether groups. The polymeric acid may be a polyether, for example, a polyether prepared by ring-opening polymerization of cyclic ether groups, such as epoxides and oxetanes. Examples of suitable epoxides include ethylene oxide, propylene oxide, glycidyl ether, glycidyl ester, and mixtures thereof. Suitable oxetanes include unsubstituted oxetanes or substituted oxetanes, such as trimethylolpropane oxetane. The polymerization of hydroxyl-functional cyclic ethers can result in a branched polyether structure.

[0030] In a further embodiment, the polymeric acid contains ester groups and ether groups. In one embodiment, the polymeric acid may be a block polymer containing at least one polyether block and at least one polyester block. Alternatively, the ester groups and ether groups may be randomly distributed.

[0031] The acidic groups may be introduced into the polymer by known methods.

[0032] The acidic phosphate esters are suitably prepared by reacting one phosphoric acid equivalent of an ester-forming phosphorus compound with 1 to 2 equivalents of a hydroxyl-functional polymer.

[0033] When one equivalent of a monohydroxyl-functional polymer is used for each phosphoric acid equivalent of the ester-forming phosphorus compound, a monoester is formed. When two equivalents are used, a diester is formed. When an equivalent between 1 and 2 is used, a mixture of monoester and diester is formed.

[0034] As used in this disclosure, the term "ester-forming phosphorus compound" is understood to refer to a phosphorus compound capable of forming a phosphate ester by reaction with a hydroxy compound. For example, phosphorus oxychloride (phosphoryl chloride), phosphorus pentoxide, polyphosphoric acid, and acetylphosphoric acid can be used as the ester-forming phosphorus compound. Additional examples are shown in German Patent Application No. DE-A2,726,854. Phosphorus pentoxide and polyphosphoric acid are preferred.

[0035] The reaction of the above ester-forming phosphorus compound with the hydroxy compound is preferably carried out without a solvent at a temperature up to about 100 °C. However, the reaction may also be carried out in the presence of a suitable inert solvent, for example, as described in European Patent Application No. EP0193019A.

[0036] Polymers having carboxylic acid groups are suitably prepared by reacting hydroxyl-functional or primary or secondary amine-functional polymers with cyclic carboxylic acid anhydrides. Examples of suitable cyclic carboxylic acid anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride, succinic anhydride, and phthalic anhydride. Alternatively, ring-opening polymerization of lactones may be initiated with a carboxylic acid to produce a carboxylic acid-functional polyester.

[0037] Polymers having sulfonic acid groups can be prepared by treating a polymer having an alkyl group with sulfur dioxide and oxygen in the presence of a radical-forming agent, by oxidation of a thio-functional polymer, or by treating a halogenated functional polymer with sodium sulfate followed by acidification.

[0038] Generally, at least 5 mol% of the tertiary amine groups of the copolymer are neutralized with an acid having a molecular weight of at least 100 g / mol. In a preferred embodiment, at least 10 mol% of the tertiary amine groups of the copolymer are neutralized. Particularly preferably, 15 - 100 mol%, most preferably 20 - 100 mol% of the tertiary amine groups are neutralized. In some embodiments, the amount of acid used for neutralization of the tertiary amine groups may be more than the theoretical amount required to neutralize 100 mol% of the tertiary amine groups. However, generally, the amount of acid is in the range of 5 - 130% of the theoretical amount required to neutralize the tertiary amine groups.

[0039] Neutralization of the tertiary amine groups may be suitably carried out by combining the copolymer with an acid and mixing these two components. The copolymer or the acid or both may be suitably provided as a solution in one or more organic solvents, thereby reducing viscosity and facilitating handling and mixing. Neutralization and salt formation are thought to be promoted by holding the composition at ambient temperature or elevated temperature for a period of time. In an exemplary embodiment, salt formation is equilibrated by holding the composition at a temperature in the range of 20 - 80 °C for 20 minutes to 24 hours after mixing.

[0040] The comb polymers of the present invention generally have a low content of quaternary amine groups or no such groups at all. In a typical embodiment, 0.0 to 4.0 mol%, preferably 0.0 to 0.5 mol% of all nitrogen atoms in the polymer are present as quaternary ammonium groups.

[0041] The comb polymers of the present invention can be suitably prepared from a base polymer having functional groups suitable for attaching side chains. In a preferred embodiment, the base polymer is a copolymer of styrene and maleic anhydride. Such copolymers can be prepared by known methods, for example, by a radical polymerization process. Copolymers of styrene and maleic anhydride are also available commercially.

[0042] The side chain group (a) can be linked to the styrene maleic anhydride-based copolymer by reacting this base copolymer with a suitable modifier (a).

[0043] In one embodiment, the modifier (a) is a polyalkylene oxide monoamine, which is a C1-C4 alcohol-initiated polyether, which is composed of ethylene oxide and / or propylene oxide and has a primary amino group: the weight ratio of ethylene oxide units to propylene oxide units is often 5:95 to 100:1, preferably 30:70 to 70:30. The number average molecular weight of the polyalkylene oxide monoamine is typically 500 g / mol to 3000 g / mol.

[0044] In a further embodiment, the modifier (a) is a monohydroxy-terminated polyether. These can be prepared, for example, by alkoxylating a monofunctional alcohol, such as an alkanol, cycloalkanol, phenol, with an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, an aliphatic or aromatic glycidyl ether, such as isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresyl glycidyl ether and phenyl glycidyl ether. Mixtures of these raw materials may also be used. In the case of mixed polyethers, they may be arranged statistically, in a stepwise form (gradient), or in blocks. These polyethers often have a number average molecular weight (Mn) in the range of about 100 to 25,000, particularly 150 to 15,000, and particularly typically 200 to 10,000 g / mol. Polyethers based on ethylene oxide, propylene oxide, or mixtures thereof are preferred.

[0045] The side chain group (b) can be linked to the styrene maleic anhydride-based copolymer by reacting this base copolymer with a suitable modifier (b).

[0046] Examples of suitable modifiers (b) include polyamine compounds having 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 amines that can be used include diethylaminopropylamine (DEAPA), dimethylaminobutylamine (DMABA), dimethylaminoethylamine (DMAEA), aminopropylmorpholine, and diisopropylaminopropylamine (DIAPA).

[0047] As described above, the copolymer of the present invention is very suitable as a wetting agent and / or dispersant for colorants.

[0048] Accordingly, the present invention further relates to a composition having the following: (A) The copolymer of the present invention (B) At least one colorant, and (C) At least one diluent.

[0049] Suitable colorants include pigments, dyes, and opacity-providing fillers, and combinations thereof.

[0050] Examples of suitable colorants are described 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 JP6248838B. Further, Pigment Red-291, Pigment Yellow-231, and Pigment Green-62, Pigment Green-63, Raven 5000 Ultra2 (a product of Birla Carbon), Raven 5000 Ultra3 (a product of Birla Carbon), COLOUR BLACK FW 100 (a product of Orion Engineered Carbons), COLOUR BLACK FW 171 (a product of Orion Engineered Carbons), COLOUR BLACK FW 200 (a product of Orion Engineered Carbons), COLOUR BLACK FW 255 (a product of Orion Engineered Carbons), COLOUR BLACK FW 310 (a product of Orion Engineered Carbons), Denka Black, and other carbon blacks used in battery applications, single-walled carbon nanotubes or multi-walled carbon nanotubes may be mentioned as very suitable colorants.

[0051] The composition further 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 dialkyl ketones, alkyl esters of alkane carboxylic acids and alkanols, especially such liquids having a total of 6 to 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 isoamyl ketone, methyl n-amyl ketone and cyclohexanone; alkyl esters, such as methyl acetate (methyl acetate), ethyl acetate (ethyl acetate), isopropyl acetate (isopropyl acetate), butyl acetate (butyl acetate), ethyl formate, methyl propionate (methyl propionate), methoxypropyl acetate, and ethyl butyrate (ethyl butyrate); glycols and glycol esters and glycol ethers, such as ethylene glycol, 2-ethoxyethanol, 3-methoxypropyl propanol, 3-ethoxypropyl propanol, 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 and cyclic ethers, such as diethyl ether and tetrahydrofuran, are included.

[0052] In a further embodiment, 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., linear and branched aliphatic hydrocarbons containing 6 or more carbon atoms, either fully or partially saturated), halogenated aliphatic hydrocarbons (e.g., dichloromethane, carbon tetrachloride, chloroform, trichloroethane), and natural non-polar organic substances such as vegetable oils, sunflower oil, linseed oil, terpenes, and glycerides.

[0053] Further examples of organic liquids include so-called reactive diluents. A reactive diluent is an organic liquid having functional groups capable of participating in a chemical curing reaction. Examples of reactive diluents include glycidyl ethers and glycidyl esters having one or more epoxy groups, and esters of acrylic acid or methacrylic acid having one or more (meth)acryloyl groups.

[0054] If desired, additional components may be included in the composition. Examples of additional components include film-forming binders, other resins and polymers, reactive diluents and solvents, curing catalysts, and further additives. The selection of additional components depends on the intended use of the colored composition. In an exemplary embodiment, the colored composition is formulated as an inkjet ink composition, as an automotive basecoat composition, or as a composition for a color filter, particularly as a color filter for a flat panel display.

[0055] The composition, which is a coating composition or an ink, can be used in various application fields, for example, automotive coatings, building coatings, protective coatings (such as marine or bridge coatings), coatings for cans and coils, coatings for wood and furniture, industrial coatings, plastic coatings, wire enamels, coatings for food and seeds, or leather coatings (both natural and synthetic leather). Examples of coating materials include paste materials, which typically contain 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, gold bronze such as bronze, iron oxide - aluminum), and other examples of effect pigments are interference pigments and pearlescent pigments, such as metal oxide - mica pigments, bismuth chloride oxide or basic lead carbonate.

[0056] When formulating a composition having a color as a color filter composition, preferably, an alkali - soluble resin is contained in the composition. Examples of suitable alkali - soluble resins are described on page 14, line 20 to page 15, line 21 of International Patent Application PCT / EP2018 / 081346 and on page 11, line 20 to page 13, line 6 of JP6248838B.

[0057] The composition for a color filter for a flat panel display preferably also contains an ethylenically unsaturated component having one or more ethylenically unsaturated groups. Examples of such components are described on page 15, line 23 to page 16, line 33 of International Patent Application PCT / EP2018 / 081346.

[0058] Preferably, the composition further comprises a film - forming binder (D).

[0059] By way of example, this film - forming binder can be any suitable organic polymer depending on the intended use of the composition. The film - forming binder can be selected from any suitable thermoplastic polymer and any suitable cross - linkable polymer.

[0060] Examples of suitable thermoplastic polymers are poly(meth)acrylate, polyacrylonitrile, polystyrene, styrenic plastics (e.g., ABS, SEBS, SBS), polyester, polyvinyl ester, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, thermoplastic polyurethane (TPU), polyvinyl chloride, polyoxymethylene, polyethylene or polypropylene.

[0061] The crosslinkable film-forming binder as defined in the present disclosure has at least one crosslinkable functional group. Any conventional crosslinkable functional group known to those skilled in the art can be contemplated in this description. More particularly suitable crosslinkable functional groups include hydroxyl group, amino group, carboxylic acid group, and unsaturated carbon double bond, isocyanate, polyisocyanate, and epoxide, for example, glycidyl ether. The crosslinkable film-forming binder may be exothermically or endothermically crosslinkable or curable. The crosslinkable film-forming binder is preferably crosslinkable or curable in the temperature range of -20 °C to 250 °C. The crosslinkable film-forming binder is preferably selected from at least one of epoxy resin, polyester (the polyester may be unsaturated), vinyl ester resin, poly(meth)acrylate, polyurethane, polyurea, polyamide, polystyrene, polyether, polycarbonate, polyisocyanate, and melamine formaldehyde resin. Such film-forming binders and their preparation are known to those skilled in the art.

[0062] The present invention further relates to the use of the copolymer according to the present invention as a wetting agent and / or dispersing agent for solid particles.

[0063] Preferably, as described above, the solid particles comprise at least one of pigments, dyes, and fillers.

[0064] The present invention also relates to a method for dispersing solid particles in a dispersion medium, wherein the comb polymer of the present invention is contained in the dispersion medium. This method typically includes mixing solid particles, the comb polymer of the present invention, and the dispersion medium while applying a shearing force.

Examples

[0065] Raw materials SMA 1000: Styrene maleic anhydride copolymer (molar ratio of styrene / maleic anhydride = 1 / 1) (Polyscope) SMA 2000: Styrene maleic anhydride copolymer (molar ratio of styrene / maleic anhydride = 2 / 1) (Polyscope) SMA 3000: Styrene maleic anhydride copolymer (molar ratio of styrene / maleic anhydride = 3 / 1) (Polyscope) Styrene: (Sigma-Aldrich) Maleic anhydride: (Sigma-Aldrich) α-MSD: α-Methylstyrene dimer (Sigma-Aldrich) AMBN: 2,2´-Azobis(2-methylbutyronitrile) (Sigma-Aldrich) PMA: 1-Methoxy-2-propyl acetate (DOW Chemical) PM: 1-Methoxy-2-propyl alcohol (DOW Chemical) Jeffamine M 2070: Amine-terminated EO / PO polyether (Huntsman) Jeffamine M 2005: Amine-terminated EO / PO polyether (Huntsman) DMAPA: N,N-Dimethylaminopropylamine (Huntsman) BzCl: Benzyl chloride (Sigma-Aldrich) BzBr: Benzyl bromide (Sigma-Aldrich) Lutensol AO11: C13-C15 alkoxylated polyethylene glycol (number of ethylene oxide units: 11) (BASF) MPEG-350: Methoxypolyethylene glycol (number of ethylene oxide units: 8) (Sigma-Aldrich) ε-Caprolactone: (Sigma-Aldrich) δ-Valerolactone: (Sigma-Aldrich) KOH: Potassium hydroxide (Sigma-Aldrich) DBSA: Dodecylbenzenesulfonic acid (Sigma-Aldrich) Phosmer M: (2-Methacryloyloxy)ethyl phosphate (Uni-Chemical), theoretical molecular weight = 210.12 g / mol MAA Methacrylic acid (Sigma-Aldrich), theoretical molecular weight = 86.06 g / mol PTSA p-Toluenesulfonic acid, theoretical molecular weight = 172.12 g / mol BA Benzoic acid, theoretical molecular weight = 122.12 g / mol

[0066] Gel permeation chromatography (GPC) In accordance with DIN 55672-1:2007-08, at 35 °C, the number average molecular weight Mn, weight average molecular weight Mw, and molecular weight distribution were measured using a high-pressure liquid chromatography pump (WATERS 600 HPLC pump) and a refractive index detector (Waters 410). As the separation column, a combination of three Waters Styragel columns with a size of 300 mm × 7.8 mm ID / column, a particle size of 5 μm, and pore sizes HR4, HR2, and HR1 was used. The eluent used was tetrahydrofuran containing 1% by volume of dibutylamine at an elution rate of 1 mL / min. Conventional calibration was performed using polystyrene standards.

[0067] Measurement of non-volatile content (solid content) The sample (1.0 ± 0.2 g of the test substance) was accurately weighed into a pre-dried aluminum dish, and about 2 ml of ethanol was added. After homogenization, it was dried at 150 °C for 20 minutes in a lacquer drying cabinet, cooled in a desiccator, and then weighed again. The residue corresponds to the solid content in the sample (ISO 3251).

[0068] Measurement of amine value 1.5 - 3.0 g of the sample was accurately weighed into an 80 mL beaker and dissolved in 50 mL of acetic acid. This solution was neutralized and titrated with 0.1 mol / L HClO4 acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve was used as the titration end point, and the amine value was determined by the following formula. Amine value [mg KOH / g] = (561 × 0.1 × f × V) / (W × S) (where f: coefficient of the titrant, V: titrant volume at the titration end point [mL], W: weighed amount of the sample [g], S: solid content concentration of the sample [wt%])

[0069] Measurement of acid value 1.5 - 3.0 g of the sample was accurately weighed into an 80 mL beaker and dissolved in 50 mL of ethanol. This solution was neutralized and titrated with 0.1 mol / L ethanol KOH solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve was used as the titration end point, and the amine value was determined by the following formula. Acid value [mg KOH / g] = (561×0.1×f×V) / (W×S) (In the formula, f: coefficient of the titrant, V: titration volume at the end point of titration [mL], W: weighed amount of the sample [g], S: solid content concentration of the sample [wt%])

[0070] Measurement of total acid value Accurately weigh 1.5 - 3.0 g of the sample into an 80 mL beaker, and dissolve it in 40 mL of pyridine and 10 mL of deionized water. Fit the 80 mL beaker with a lid, and heat it at 70 °C for 60 minutes in a thermostat or a water bath with stirring. After cooling, neutralize and titrate the solution with 0.1 mol / L NaOH aqueous solution using an automatic titrator equipped with a pH electrode. Use the inflection point of the titration pH curve as the end point of titration, and calculate the amine value according to the following formula. Total acid value [mg KOH / g] = (561×0.1×f×V) / (W×S) (In the formula, f: coefficient of the titrant, V: titration volume at the end point of titration [mL], W: weighed amount of the sample [g], S: solid content concentration of the sample [wt%])

[0071] Synthesis of styrene - maleic anhydride copolymer (I - SMA 1000 / I - SMA 1081) Add 51.4 g of PMA to the reaction vessel and heat it to 120 °C with stirring. Then, dropwise add 18.3 g of maleic anhydride, 19.5 g of styrene, and 2.1 g of AMBN dissolved in 8.7 g of PMA to the reaction vessel. React at 120 °C for 1 hour. After cooling, obtain styrene - maleic anhydride copolymer (I - SMA 1000).

[0072] I - SMA 1000 had a solid content of 40% and a total acid value of 211 mg KOH / g.

[0073] Synthesis of styrene - maleic anhydride copolymer (I - SMA 2000) 3.7 g of α-MSD and 37.9 g of PMA were added to a reaction vessel and heated to 130 °C with stirring. Subsequently, 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.

[0074] I-SMA 2000 had a solid content of 47.5% and a total acid value of 150 mg KOH / g.

[0075] Synthesis of amine comb copolymer C-1 39.5 g of I-SMA 2000 was added to a reaction vessel and the mixture was heated to 70 °C with stirring. Subsequently, 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.

[0076] Synthesis of amine comb copolymers C-2 to C-8 The synthesis of amine comb copolymers C-2 to C-8 was carried out using the same procedure as that used for amine comb copolymer C-1, except that different types and amounts of monomers related to the side chain, pigment affinity groups, and additional solvents were used as required (details are described in Table 1).

[0077] Synthesis of amine random copolymer RC-1 85.0 g of PMA was added to a reaction vessel. Next, 52.8 g of SMA 1000 was added during stirring and the mixture was heated to 70 °C. Subsequently, 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.

[0078] Synthesis of quaternized comb copolymer QC-1 38.5 g of comb-shaped copolymer C-1, 58.6 g of PMA, and 2.9 g of benzyl chloride were added to a reaction vessel, and the reaction vessel was heated to 120 °C. The quaternization reaction was carried out at 120 °C for 4 hours. Thereafter, quaternized comb-shaped copolymer QC-1 was obtained.

[0079] The quaternized comb copolymer QC-1 had a solid content of 40% and an amine value of 4 mg KOH / g of the polymer.

[0080] Synthesis of Quaternized Comb-shaped Copolymers QC-2 to QC-4 Quaternized comb-shaped copolymers QC-2 to QC-6 were synthesized using the same procedure as that used for quaternized comb-shaped copolymer QC-1, except that different types and amounts of quaternizing agents and solvents were used (details are described in Table 2).

[0081] Preparation of Aqueous Medium Comb-shaped Copolymer WC-1 50.0 g of comb-shaped copolymer C-1 and 50.0 g of deionized water were added to a reaction vessel, and the reaction vessel was heated at 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 the distillation operation was carried out several times. After adding an appropriate amount of deionized water to adjust the solid content, aqueous medium comb-shaped copolymer WC-1 was obtained.

[0082] The aqueous medium comb-shaped copolymer WC-1 had a solid content of 40% and an amine value of 36 mg KOH / g of the polymer.

[0083] Synthesis of Acidic Polymer AP-1 0.3 g of KOH, 77.5 g of MPEG-350, and 22.2 g of succinic anhydride were added to a reaction vessel, and the reaction vessel was heated to 80 °C. The synthesis of acidic polymer AP-1 was carried out at 80 °C for 1 hour.

[0084] The acidic polymer AP-1 had a solid content of 100%, an acid value of 124 mg KOH / g of the polymer, and a theoretical molecular weight of 450 g / mol.

[0085] Synthesis of Acidic Polymer AP-2 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 acidic polymer AP-2 was carried out at 80°C for 1 hour.

[0086] Acidic polymer AP-2 had 100% solids content, an acid value of 186 mg KOH / g of polymer, and a theoretical molecular weight of 772 g / mol.

[0087] Synthesis of Acidic Polymer AP-3 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 acidic polymer AP-3 was carried out at 80°C for 1 hour.

[0088] Acidic polymer AP-1 had 100% solids content, an acid value of 125 mg KOH / g of polymer, and a theoretical molecular weight of 448 g / mol.

[0089] Synthesis of Acidic Polymer AP-4 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 reaction vessel was heated to 80°C. The reaction was carried out at 80°C for 1 hour. Then, 12.4 g of succinic anhydride and 0.3 g of KOH were added to the reaction vessel. The synthesis of acidic polymer AP-4 was carried out at 80°C for 1 hour.

[0090] Acidic polymer AP-4 had 100% solids content, an acid value of 70 mg KOH / g of polymer, and a theoretical molecular weight of 780 g / mol.

[0091] Synthesis of Acidic Polymer AP-5 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 a reaction vessel, and the reaction vessel was heated to 80°C. The reaction was carried out at 80°C for 1 hour. Then, 10.3 g of PPA was added to the reaction vessel. The synthesis of acidic polymer AP-5 was carried out at 80°C for 1 hour.

[0092] The acidic polymer AP-5 had a solids content of 100%, an acid value of 137 mg KOH / g of polymer, and a theoretical molecular weight of 875 g / mol.

[0093] Synthesis of neutralization product S-1 30.9 g of amine-comb copolymer C-1, 9.2 g of acidic 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.

[0094] Synthesis of neutralization products S-2 to S-24 The neutralization products S-2 to S-24 were synthesized using the same procedure as that used for the neutralization product S-1, except that different types of amine-comb copolymers, acidic polymers and components, different molar ratios of amine to acid, and different dosages of solvent and deionized water were used (details are shown in Table 4).

[0095] Synthesis of alkali-soluble resin B1 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 metered at a temperature of 120°C over 180 minutes. The reaction time after the metering was 120 minutes. Then, using PMA, the solids content was adjusted to 35% by weight (DIN EN ISO 3251:2008-06, 20 minutes at 150°C). The number average molecular weight was 7875 g / mol.

[0096]

Table 1

[0097]

Table 2

[0098]

Table 3

[0099]

Table 4

[0100] Preparation of Pigment Composition

[0101] Manufacture of Red, Green, and Blue Dispersions for Use in Color Filter Applications PG-58: Fastogen Green A110 (DIC) PR-254: Irgaphor Red BT-CF (BASF) PB-15:6: Fastogen Genblue EP-193 (DIC)

[0102] General Manufacturing Procedure for Dispersion R-1 Used in Color Filter Applications 4.3 g of alkali-soluble resin B1 and 9.4 g of dispersant S-1 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. Next, 7.5 g of PR-254 and 150 g of zirconia beads (diameter: 0.4 - 0.6 mm) were added to the glass bottle. The dispersion process was carried out at 30 °C for 5 hours in a LAU-Disperser DAS 200. After 5 hours, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0103] General Manufacturing Procedure for Dispersions R-2 to R-5, G-1 to G-8, and B-1 to B-4 Used in Color Filter Applications Dispersions R-2 to R6, G-1 to G-9, and B-1 to B-5 were prepared according to the procedure for Dispersion R-1 (details are described in Table 5).

[0104]

Table 5

[0105] Manufacture of Resist Ink BYK-330: Silicone-based Additive (BYK-Chemie) Aronix M305: Pentaerythritol Triacrylate (TOA GOSEI) Omnirad 369: Former Name: Irgacure 369, 2-Benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone (IGM Resins B.V.)

[0106] The formulation (recipe) of the resist ink is described as follows; Dispersion 50.0 g 2% BYK-330 PMA Solution 1.0 g Alkali-soluble Resin B1 14.2 g Aronix M305 2.0 g Omnirad 369 1.0 g PMA 31.8 g Total 100.0 g

[0107] Application Test Results

[0108] Viscosity of Red, Green and Blue Dispersions The viscosities of the red, green and blue dispersions were measured using a BROOKFIELD VISCOMETER DV-II+ (BROOKFIELD, Viscosity Upper Limit: 1000 mPa·s).

[0109] Particle Size of Red, Green and Blue Dispersions: The particle sizes (median diameter: D50) of the red, green and blue dispersions were measured using a particle size analyzer ELSZ-1000 (Otsuka Electronics).

[0110] Development Characteristics Using a bar coater No. 4 (thickness in wet film: 9.16 μm), red, green, and blue resist inks were applied to a glass plate, and the coating film was dried at 80 °C for 3 minutes. The dried coating film was gradually immersed in a 0.05% KOH aqueous solution (interval: 10 - 60 seconds). After washing these, the coating film was wiped off using KimWipes (a product of Kimberly Clark Corporation), and the appearance of the coating film was recorded as described below; 1 (Excellent): After wiping, the coating film completely disappeared 2 (Very good): After wiping, the coating film was partially removed 3 (Good): The coating film was not removed, but the surface of the coating film was almost removed after wiping 4 (Poor): The coating film was not removed, but the surface of the coating film was partially removed after wiping 5 (Bad): The appearance of the coating film did not change after wiping

[0111] Redissolution in PMA Using a bar coater No. 4 (thickness in wet film: 9.16 μm), red, green, and blue resist inks were applied to a glass plate, and the coating film was dried at 80 °C for 3 minutes. One drop of a PMA droplet was placed on the coating film and immediately wiped off using a Kimwipe. The appearance of the coating film after wiping was recorded as follows; 1 (Excellent): After wiping, the coating film in a trace amount of PMA droplet was completely removed 2 (Very good): After wiping, the coating film in a trace amount of PMA droplet was partially removed 3 (Good): After wiping, the coating film in a trace amount of PMA was not removed, but the surface of the coating film was almost removed 4 (Poor): After wiping, the coating film in a trace amount of PMA was not removed, but the surface of the coating film was partially removed 5 (Bad): The appearance of the coating film did not change after wiping

[0112] Examples 1 - 10: Viscosity and particle size of red (R), green (G), and blue (B) dispersions, and development characteristics and redissolution in PMA of red (R), green (G), and blue (B) resist inks The viscosities (mPa·s at 20°C, rotation speed: 60 rpm) and particle sizes (D50) of the red, green, and blue dispersions, as well as the development characteristics and re-dissolvability in PMA of the red, green, and blue resist inks, are described in Table 6.

[0113]

Table 6

[0114] Comparative Examples C-1 to C-7: Viscosities and particle sizes of the red (R), green (G), and blue (B) dispersions, as well as development characteristics and re-dissolvability in PMA of the red, green, and blue resist inks;

[0115] The viscosities (mPa·s at 20 °C, rotation speed: 60 rpm) and particle sizes (D50) of the red, green, and blue dispersions are described in Table 8, and the development characteristics and re-dissolvability in PMA of the red, green, and blue resist inks are described in Table 7.

[0116]

Table 7

[0117] According to the results in Tables 6 and 7, the red, green, and blue dispersions containing the neutralization products between the amine copolymer and the acidic polymer showed excellent dispersibility and storage stability (Examples 1 to 10). Furthermore, the red, green, and blue resist inks containing these dispersions also showed excellent development characteristics and re-dissolvability in PMA.

[0118] However, the green dispersions (Comparative Examples C-3, C-4) containing the neutralization products between the amine-comb copolymer and the low-molecular-weight acidic component showed poor storage stability, and their resist inks showed poor development characteristics and re-dissolvability in PMA.

[0119] The red dispersion (Comparative Example C-1) containing the neutralization product between the amine (non-comb type) copolymer and the acidic polymer or the low-molecular-weight acidic component showed poor dispersibility.

[0120] The green dispersions containing the amine comb copolymer (Comparative Example C-6) and the quaternized comb copolymer (Comparative Example C-5) showed poor dispersibility.

[0121] The red and blue dispersions containing the quaternized comb copolymer (Comparative Examples C-2 and C-7) showed relatively good dispersibility and storage stability, but their resist inks showed poor redissolubility in PMA.

[0122] Manufacture of Carbon Black Dispersions for Solvent-Based Jet Black Coatings Raven U3: Raven 5000 Ultra 3 (Birla Carbon) PMA: 1-Methoxy-2-propyl acetate (DOW Chemicals)

[0123] General Manufacturing Procedure of Solvent-Based Carbon Black Dispersion Bk-1 9.7 g of dispersant S-1 was placed in a 140 ml glass bottle. Then, 36.0 g of PMA was added to the glass bottle to dissolve the dispersant in PMA. Next, 4.3 g of Raven 5000 Ultra 3 (Raven U3) and 150 g of zirconia beads (diameter: 0.4 - 0.6 mm) were added to the glass bottle. The dispersion process was carried out at 30 °C for 10 hours in a LAU-Disperser DAS 20. After 10 hours, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0124] General Manufacturing Procedure of Carbon Black Solvent-Based Dispersions Bk-2 to Bk-6 The solvent-based dispersions Bk-2 to Bk-6 followed the procedure of dispersion Bk-1 (details are described in Table 8).

[0125]

Table 8

[0126] Examples 11 - 13: Viscosity and Particle Size of Solvent-Based Carbon Black Dispersions Bk-1, Bk-3, and Bk-4 The viscosities (mPa·s at 20°C, rotation speed: 60 rpm) and particle sizes (D50) of the solvent-based carbon black dispersions Bk-1, Bk-2, and Bk-4 were described in Table 9.

[0127]

Table 9

[0128] Comparative Examples 8-10: Viscosities and Particle Sizes of Solvent-Based Carbon Black Dispersions Bk-2, Bk-5, and Bk-6 The viscosities (mPa·s at 20°C, rotation speed: 60 rpm) and particle sizes (D50) of the solvent-based carbon black dispersions Bk-2, Bk-5, and Bk-6 were described in Table 10.

[0129]

Table 10

[0130] According to the results in Tables 9 and 10, the solvent-based black dispersions containing the neutralized product between the amine-like comb copolymer and the acidic polymer showed promising results as the solvent-based carbon black dispersions used for the coatings of transportation vehicles (Examples 11 to 13).

[0131] On the other hand, the black dispersion containing the neutralized product between the amine-like comb copolymer and the low-molecular-weight acidic component (Comparative Example C-8) and the black dispersion containing the quaternized comb-like copolymer (Comparative Example C-9) showed poor storage stability. Also, the black dispersion containing the amine comb-like copolymer (Comparative Example C-10) showed poor dispersibility.

[0132] Production of Blue Dispersions Used for Aqueous Medium Blue Coatings G314: Cyanine Blue G-314 (SANYO COLOR) BYK-011: Polymer-based Antifoaming Agent (BYK-Chemie) DYN 800N: BYK-DYNWET 800N, Wetting Agent (BYK-Chemie)

[0133] General manufacturing procedure of aqueous medium blue dispersion Bl-1 31.4 g of deionized water, 0.3 g of BYK-011 and 0.80 g of BYK-DYNWET 800N were placed in a 140 ml glass bottle. Then, 7.50 g of dispersant S-15 was added to the glass bottle to dissolve the dispersant in deionized water. Subsequently, 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. The dispersion process was carried out at 30 °C for 8 hours in a LAU-Disperser DAS 200. After grinding, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0134] General manufacturing procedure of aqueous medium blue dispersions Bl-2 to Bl-4 The aqueous medium blue dispersions Bl-2 to Bl-4 were prepared according to the procedure of dispersion Bl-1 (details are described in Table 11).

[0135] [Table 11]

[0136] Examples 14 - 15: Viscosity and particle size of aqueous medium blue dispersions Bl-1 to Bl-2 The viscosities (mPa·s at 20 °C, rotation speed: 60 rpm) and particle sizes (D50) of the aqueous medium blue dispersions Bl-1 to Bl-2 are listed in Table 12.

[0137] [Table 12]

[0138] Comparative Examples 11 - 12: Viscosity and particle size of aqueous medium blue dispersions Bl-3 to Bl-4 The viscosities (mPa·s at 20 °C, rotation speed: 60 rpm) and particle sizes (D50) of the aqueous medium blue dispersions Bl-3 to Bl-4 are listed in Table 13.

[0139] [Table 13]

[0140] According to the results of Tables 12 and 13, the aqueous medium blue dispersion containing the neutralization product between the amine comb copolymer and the acidic polymer showed promising results as the aqueous medium blue dispersion used for the coating of the transport vehicle (Examples 14 to 15).

[0141] On the other hand, the blue dispersion containing the neutralization product between the amine comb copolymer and the low molecular weight acidic component (Comparative Example C-11) showed poor storage stability. Further, the blue dispersion containing the amine comb copolymer (Comparative Example C-12) showed poor dispersibility.

[0142] Manufacture of the black dispersion used for battery applications Denka Black: Denka Black (granular) (Denka) BYK-017: Polymer type antifoaming agent (BYK-Chemie)

[0143] General manufacturing procedure of the aqueous medium black dispersion WBk-1 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 the dispersant S-15 was added to the glass bottle to dissolve the dispersant in 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. The dispersion process was carried out at 30 °C for 3 hours in a LAU-Disperser DAS 200. After pulverization, the concentrate was filtered into a 50 ml glass bottle to remove the zirconia beads.

[0144] General manufacturing procedure of the aqueous medium black dispersions WBk-2 to WBk-4 The aqueous medium black dispersions WBk-2 to WBk-4 were prepared according to the procedure of the dispersion WBk-1 (details are described in Table 14).

[0145]

Table 14

[0146] Example 16 - 17: Viscosity and Particle Size of Aqueous Medium Black Dispersions WBk - 1 to WBk - 2 The viscosities (mPa·s at 20°C, rotation speeds: 60 rpm and 6 rpm) and particle sizes (D50) of the aqueous medium black dispersions WBk - 1 to WBk - 2 are shown in Table 15.

[0147] [Table 15]

[0148] Comparative Examples 13 - 14: Viscosity and Particle Size of Aqueous Medium Black Dispersions WBk - 3 to WBk - 4 The viscosities (mPa·s at 20°C, rotation speeds: 60 rpm and 6 rpm) and particle sizes (D50) of the aqueous medium black dispersions WBk - 3 to WBk - 4 are shown in Table 16.

[0149] [Table 16]

[0150] According to the results in Tables 15 and 16, the aqueous medium black dispersions containing the neutralization product between the amine comb - shaped copolymer and the acidic polymer showed promising results as the aqueous medium black dispersions used in lithium - ion batteries (Examples 16 - 17).

[0151] On the other hand, the black dispersion containing the neutralization product of the amine comb - shaped copolymer and the low - molecular - weight acidic component (Comparative Example C - 13) showed a thixotropic phenomenon. Also, the black dispersion containing the comb - shaped copolymer (Comparative Example C - 14) showed poor dispersibility and viscosity.

[0152] Production of Blue Dispersions for Solvent - Based Blue Coatings Heliogen Blue L7110F beta - phthalocyanine blue organic pigment (BASF) Ethanol Ethyl acetate

[0153] General Production Procedure of Solvent - Based Blue Dispersion SB - 1 29.4 g of a 9:1 mixture of ethanol / ethyl acetate was placed in a 100 ml glass bottle, and 5.6 g of dispersant S-17 was added. Subsequently, 15.0 g of Heliogen Blue L7110F and 50 g of zirconia beads (1.0 - 1.3 mm in diameter) were added to the glass bottle. The dispersion process was carried out in a LAU-Disperser DAS 200 for 60 minutes.

[0154] General manufacturing procedure for solvent-based blue dispersions SB-2 to SB-11 The solvent-based blue dispersions SB-2 to SB-11 were prepared according to the procedure for dispersion SB-1 (details are described in Table 17).

[0155]

Table 17

[0156] Examples 18 - 24: Viscosity and particle size of solvent-based blue dispersions SB-1 to SB-7 The viscosities of the solvent-based blue dispersions SB-1 to SB-7 are described in Table 18.

[0157]

Table 18

[0158] Comparative Examples 15 - 18: Viscosity and particle size of solvent-based blue dispersions SB-8 to SB-11 The viscosities and particle sizes of the solvent-based blue dispersions SB-8 to SB-11 are described in Table 19.

[0159]

Table 19

[0160] According to the results in Tables 18 and 19, the solvent-based blue dispersions containing the neutralization product between the amine comb copolymer and the acidic polymer showed promising results as solvent-based blue dispersions used in printing inks (Examples 18 - 25).

[0161] On the one hand, the blue dispersion (Comparative Example C-15) containing a neutralized product of an amine copolymer and a low molecular weight acidic component showed a relatively high viscosity. Also, the blue dispersions (Comparative Examples C-16-18) containing an amine copolymer showed relatively poor dispersibility. The present disclosure includes the following aspects of the invention: <Aspect 1> A comb copolymer having a polymer backbone and lateral side chains linked to the polymer backbone, wherein the lateral side chains are (a) alkyl ether-terminated polyalkylene oxide side chains, and (b) tertiary amine-functional side chains, wherein the tertiary amine groups are at least partially neutralized by an acid having a molecular weight in the range of 100 g / mol to 2000 g / mol, and the molecular weight is related to the number average molecular weight Mn in the case of a polymeric acid, the tertiary amine-functional side chains being included, wherein the lateral side chains (a) and (b) are distributed in a random order, a comb copolymer. <Aspect 2> The comb copolymer according to Aspect 1, wherein the acid has a molecular weight in the range of 150 to 2000 g / mol, and the molecular weight is related to the number average molecular weight Mn in the case of a polymeric acid. <Aspect 3> The comb copolymer according to Aspect 1 or 2, wherein the acid contains an acid group including at least one of a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group. <Aspect 4> The comb copolymer according to any one of Aspects 1 to 3, wherein the acid contains a polyether moiety or a polyester moiety. <Aspect 5> The comb copolymer according to any one of Aspects 1 to 4, wherein at least 5 mol% of the tertiary amine groups are neutralized by an acid having a molecular weight in the range of 100 g / mol to 2000 g / mol, and the molecular weight is related to the number average molecular weight Mn in the case of a polymeric acid. <Aspect 6> The comb copolymer according to any one of Aspects 1 to 5, wherein the alkyl ether-terminated polyalkylene oxide side chains are linked to the polymer backbone via an imide group. <Aspect 7> The comb copolymer according to any one of Aspects 1 to 6, wherein the amine-functional side chains are linked to the polymer backbone via an imide group. <Aspect 8> The comb copolymer according to any one of Aspects 1 to 7, wherein the polymer backbone has polymerized units of a vinyl aromatic hydrocarbon monomer. <Aspect 9> The comb copolymer according to any one of Aspects 1 to 8, wherein the polymer backbone has polymerized units of an N-substituted maleimide. <Aspect 10> The comb copolymer according to any one of Aspects 1 to 9, wherein the amine value of the polymer is in the range of 5 to 150 mg KOH / g. <Aspect 11> (A) The comb copolymer according to any one of Aspects 1 to 10 (B) at least one colorant, and (C) at least one diluent, A composition containing <Aspect 12> The composition according to aspect 11, further containing a film-forming binder (D). <Aspect 13> Use of the comb polymer according to any one of aspects 1 to 10 as a wetting agent and / or dispersant for solid particles. <Aspect 14> The use according to aspect 13, wherein the solid particles contain at least one of a pigment, a dye, and a filler. <Aspect 15> A method for dispersing solid particles in a liquid dispersion medium, wherein the comb polymer according to any one of aspects 1 to 10 is present in the dispersion medium.

Claims

1. A comb copolymer having a polymer backbone having polymerized units of vinyl aromatic hydrocarbons and having lateral side chains linked to the polymer backbone, wherein the lateral side chains are (a) alkyl ether-terminated polyalkylene oxide side chains, and (b) tertiary amine-functional side chains, wherein at least 5 mol% of the tertiary amine groups are neutralized by an acid having a molecular weight in the range of 100 g / mol to 2000 g / mol, and in the case of a polymeric acid, the acid contains a polyether moiety or a polyester moiety, and the molecular weight is related to the number average molecular weight Mn determined by gel permeation chromatography using a polystyrene standard for calibration, tertiary amine-functional side chains including the lateral side chains (a) and (b) being distributed in a random order, comb copolymer.

2. The comb copolymer according to claim 1, wherein the acid has a molecular weight in the range of 150 to 2000 g / mol, and the molecular weight is related to the number average molecular weight Mn in the case of a polymeric acid.

3. The comb copolymer according to claim 1 or 2, wherein the acid contains an acid group containing at least one of a carboxylic acid group, a phosphoric acid group, and a sulfonic acid group.

4. The comb copolymer according to claim 1 or 2, wherein the alkyl ether-terminated polyalkylene oxide side chain is linked to the polymer backbone via an imide group.

5. The comb copolymer according to claim 1 or 2, wherein the amine-functional side chain is linked to the polymer backbone via an imide group.

6. The comb copolymer according to claim 1 or 2, wherein the polymer backbone has polymerized units of N-substituted maleimide.

7. The comb copolymer according to claim 1 or 2, wherein the amine value of the polymer is in the range of 5 to 150 mg KOH / g.

8. (A) The comb copolymer according to claim 1 or 2 (B) at least one colorant, and (C) at least one diluent, a composition containing.

9. The composition according to claim 8, wherein the composition further contains a film-forming binder (D).

10. Use of the comb copolymer according to claim 1 or 2 as a wetting agent and / or dispersant for solid particles.

11. The use according to claim 10, wherein the solid particles include at least one of a pigment, a dye, and a filler.

12. A method for dispersing solid particles in a liquid dispersion medium, wherein the comb polymer according to claim 1 or 2 is present in the dispersion medium.

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