TWI323673B - Dispersants - Google Patents

Description

A7 B7 Five inventions (1) Dispersant can be derived from polyvinylamine 'polyallylamine or a PAI having at least two primary or tertiary amine groups and a TPOAC acid, in this case polyvinylamine, polypropylamine or PAI The reaction product of the internal amine group and the terminal carboxylic acid of the p〇AC acid forms a chiral amine or a salt bond. If the PAI contains a tertiary amine group, only a salt bond can be formed, or a salt and/or a guanamine bond can be formed depending on the reaction conditions. Generally mild reaction conditions such as low temperature and/or short reaction time promote the formation of a salt bond. The more severe reaction conditions, such as high temperature and/or long reaction time, promote the formation of a guanamine bond in a manner well known to the skilled chemist. When the dispersing agent contains a free amine group, it can be converted into a substituted ammonium group by an acid or a quenching agent to form a substituted ammonium salt. Suitable reagents for this use are inorganic acids and strong organic acids or acidic salts such as acetic acid and sulfuric acid. , hydrochloric acid, alkyl sulfonic acid, hydrogen sulphate and aryl sulfonic acid including dyes and pigments of acid and quaternizing agents such as dialkyl sulfate such as dimethyl sulfate (DMS) and alkyl amides such as methyl and Ethyl chloride. Dispersion of the first case of the present invention It can be obtained by reacting polyacetamide, polyallylamine or p AI with a TPOAC acid or its lactone at a temperature of 50-250 ° C, preferably in an inert atmosphere and optionally having an esterification solvent. Not less than 8 ° C, especially not less than 10 ° C. For the final reduction of dispersant coking, the temperature should not exceed 150 ° C. The inert atmosphere can be any gas that does not react with the final product or the starting material, including Inert gas of the periodic table, especially nitrogen. In the single stage, polyvinylamine, polyallylamine or PAI, polymerization terminator τ-C00H and lactone (etc.) are reacted to prepare a dispersant, which preferably includes an esterification agent such as titanium. a tetraalkyl ester such as tetrabutyl titanate, a zinc salt of an organic acid such as zinc acetate, a zirconium salt of an aliphatic alcohol such as cesium isopropoxide, toluenesulfonic acid or a strong organic acid such as acetic acid such as _ -13- paper Zhang scale applies to China National Standard (CNS) A4 specification (21〇χ297 public) 1323673 A7 B7 V. Description of invention (11) Trifluoroacetic acid, etc. It is preferred to use isopropanol. The dispersant of the first case of the present invention is used. Higher temperatures may be necessary for single-stage preparation, typically from 150-1 8 (TC. Better separation of TPOAC acid) Then it is reacted with polyvinylamine, polyallylamine or PAI. In this case, the lactone (etc.) and the polymerization terminator are in an inert atmosphere at 150-1 80 °C and the esterification reaction is present in the next step. The reaction of TPOAC acid with polyvinylamine, polypropylamine or PAI can be carried out at a temperature of 100-150 ° C. The weight ratio of TPOAC acid to PEI can change within a wide range when PAI is PEI, depending on whether the dispersant Finally, it is determined by dispersing the particulate solids in a polar or non-polar organic medium. The weight ratio of TPOAC acid to PEI has been effective with dispersants from 30:1 to 1:1, preferably from 20:1 to 5:1. Especially from 17:1 to 7:1. According to a second aspect of the invention, there is provided a dispersant of formula 1 wherein Z is an acid group or comprises a moiety selected from the group consisting of a carboxylate, a sulfate, a sulfonate, a phosphate and a phosphonate. A preferred dispersant for the second aspect of the invention is a compound of formula 6. B+O-V-CO—)—D (6) η In the formula: Β and D are groups, one of which is an acidic group or has an acidic group, and the other is a branched aliphatic chain. V and η are the same as before. In the dispersant of formula 6, the acid group of D is preferably a T-CO- group of a T-COOH-type esterified carboxylic acid. In this case, D is preferably a multi-valent, more suitable for two or three-valent connection -14 - This paper scale is applicable to China National Standard (CNS) Α4 specification (210 X 297 mm) 1323673 A7 B7 V. Invention description (15) Examples of the agent are amino acids such as glycine and short chain hydroxy acids such as glycolic acid or lactic acid. The dispersant of the second aspect of the present invention can also be obtained by a two-stage indirect method in which a compound of the formula 7 is reacted with a linking compound containing at least one reactive group, a reactive group with a monocarboxylic acid group such as a hydroxyl group or an amine group, and at least another activity Upon reaction, the resulting intermediate product is then reacted with a compound containing an acidic group and a group reactive with the other reactive groups of the linking compound. Suitable linking compounds include polyols, diamines and hydroxylamines such as ethylene glycol, propylene glycol, glycerol, tris(hydroxy)propane, pentaerythritol, phytosterol, ethylenediamine, trimethyldiamine, hexamethylenediamine, Ethylene triamine, ethanolamine, diethanolamine, dipropanolamine and tris(hydroxymethyl)aminocarbyl. Preferably, the amine-linked compound is used, and the oligomeric intermediate product is reduced due to the difference in reactivity between the base group and the amine group. Suitable linking compounds containing an acidic group and the other reactive groups reactive with the compound of formula 6 include strong mineral acids such as phosphoric acid, sulfuric acid, chlorosulfonic acid and aminosulfonic acid, and organic salts such as alkyl and arylphosphonic acids, alkanes. Base and aryl sulfonic acid and monochloroacetic acid. When the dispersant of the second aspect of the invention is prepared from the compound of the formula 7, the reaction of the compound of the formula 7 with an acid group (in the direct route) or with a linking compound (by an indirect route) is carried out under conditions suitable for the reactants involved. . For example, in the case of a direct reaction of a compound of the formula 7 with a monofunctional acid such as glycine or glycolic acid, the reactants may be heated at a temperature of from 180 to 250 ° C, if necessary in the presence of a solvent such as xylene. In the presence of the aforementioned esterification catalyst until the acid value of the reaction mixture has fallen to a suitable level. Preferably, the reagent is used in an approximate stoichiometric amount relative to a hydroxyl group or an amine group in the compound of formula 7 or a group having an acidic group. The same conditions in the indirect route case apply to the reaction between the compound of formula 7 and the linking compound, except that only one reactive group is used in the latter to ensure that the obtained intermediate product still contains the -18-paper scale applicable to the Chinese National Standard (CNS) A4. Specification (210 X 297 mm) 1323673 A7 _______B7 ____ V. INSTRUCTION DESCRIPTION (16) The active group can be used for subsequent reaction with a compound having an acidic group. The reaction temperature is preferably from 150 to 200 ° C when the compound is attached. An inert solution or diluent and/or catalyst may also be used here if desired. The second-stage intermediate product of the indirect route reacts with the compound having an acidic group at a temperature for a period of time sufficient to completely react as the reaction mixture reaches a substantial acid value. When the acid group-containing compound is a polybasic acid such as phosphoric acid or sulfuric acid, one or two of the ionized hydrogen atoms are preferred, and particularly preferred, the water produced by the reaction is not intended to be removed. The reaction is usually carried out in about 3 hours at 40-70 ° C; because of the dehydration of the product, it is preferred to avoid strong conditions, especially with sulfuric acid. In the case of monochloroacetic acid, no complication occurs, but the reaction proceeds more slowly, but rather requires more aggressive conditions. Generally, an acid group-containing compound having a stoichiometric amount is used in the active material in the precursor, but it may be used in a smaller amount or more if necessary. The dispersant of the direct bond of J in Formula 8 can be obtained by reacting a POAC acid having a carboxylic acid end group with an amine group or a hydroxy organic sulfonic acid, and preferably an amine or hydroxyalkyl phosphate. The dispersing agent of formula 8 wherein J is NR or oxygen can be reacted with a POAC acid and a diol or a hydroxylamine compound such as an amino alcohol, and then the hydroxyl end group of the produced intermediate and the monophosphorylation agent such as P2〇5 or Polyphosphoric acid or a reaction with a sulfonating agent such as chlorosulfonic acid. The dispersing agent of the K-type direct bond in Formula 8 may be a TPOAC acid T C0(0-V-CO)n+p-OH (10) of the formula 10 and a compound of the formula 11 (Η-K-G) WLM (Π) -19 - This paper scale applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 1323673 A7 B7 V. Invention description (17) Reaction acquisition, T, V, K, G'L'M, n, ρ and w has the same meaning as before. The dispersant wherein K is ruthenium or NR in formula 8 is reacted with tp〇ac acid of formula 1 and reacted with a compound of formula 12, Η-Κ-G-Ο-Η (12), and then reacted with a sulfating or phosphorylating agent. obtain. A particularly preferred dispersant of formula 9 can be polymerized by the lactone (etc.) in the presence of a unit or a unit amine to form a TPOAC alcohol having a hydroxyl end group, i.e., a POAC chain having a terminal group and a polymerization end group. The unit alcohol is preferred, particularly as many as 50, particularly preferably having 36 carbon atoms. The TPOAC alcohol is then reacted with a phosphating or sulfating agent. Preferred are phosphorylating agents, especially Ρ2〇5 and polylinic acid. The TPOAC alcohol can be obtained by reacting a lactone (etc.) with a unit alcohol under the conditions similar to those used for the preparation of tp〇aC acid. The dispersant is a phosphate of the formula 9 which can be obtained by reacting a TPOAC alcohol with a linonic acid agent to obtain 'the ratio of the alcohol to the phosphorylating agent per phosphorus atom is from 3:1 to 1:1', especially from 2^:1 to 1:1. The ratio of each TPOAC alcohol to each phosphorous ion in the phosphorylating agent is particularly preferably less than 2, for example about 1.5:1 when the dispersing agent is a mono- and di-squareate mixture. The reaction of the TPOAC alcohol with the phosphorylating agent is preferably carried out in an inert atmosphere such as nitrogen under anhydrous conditions. The reaction can be carried out in an inert solvent, but the reaction of the Tp〇AC alcohol with the phosphorylating agent in the absence of a solvent is more convenient. The reaction temperature is preferably 6 Torr.匸 上 上 'Special good 8 〇. (: Above' is to avoid coking of the dispersing agent, the temperature should be lower than 12 〇. 〇, especially ll 〇 ° C below. -20-

1323673 A7 _________B7____ V. INSTRUCTIONS (20) The reaction between an amine, imine, polyamine or polyimine and a compound of formula 14 is preferably carried out between ΙΟ-ΐ 30 °C, particularly between 20 and 1 〇〇 °C. A scalar amine or an imine and a compound of formula 14 can be used. However, in the preferred embodiment of the invention, a dispersant is obtained by reacting an excess of the compound of formula 14 with a polyamine or a polyimine such as PAI, particularly PEI. The reaction between the amine, imine, polyamine or polyimine and the compound of the formula 4 can be carried out in a solvent inert to a pair of reactants. The solvent may be a genus or a genus such as toluene, dimethyl sulphate and Solvesso, hydrazines such as propyl hydrazine, methyl ethyl ketone and methyl isobutyl methacrylate, and an alcohol such as n-butanol and isopropanol and ethers. Such as adipic acid diacetic acid vinegar, dimethyl succinate and dimethyl glutarate. Many of the intermediates used in the powder preparation process according to the present invention are novel, particularly the TPOAC acid used in the first aspect of the present invention and the TPOAC alcohol in the second preferred embodiment of the present invention. Thus, a TPOAC alcohol of formula 2, a Tp〇AC acid of formula 3 and a compound of formula 14 are provided in accordance with the present invention. The previously noted dispersant is particularly useful for dispersing particulate solids in organic media. According to another aspect of the present invention, a composition comprising a particulate solid and a hydrazine dispersant is provided. - According to still another aspect of the present invention, a dispersant-package type bismuth dispersant, a particulate solid and an organic medium are provided. The solid contained in the dispersion may be any inorganic or organic solid material which is substantially insoluble in the organic medium at the temperature involved and is expected to be stabilized into a pulverized state therein. Examples of suitable solids are pigment inks; pigments, extenders and fillers for paints and plastics; dyes, special disperse dyes; optical materials and soluble -23-t ® S (CNS) A4^ (210 X 297- ^3⁄4) ---- 1323673 A7 B7 V. INSTRUCTIONS (21) Textile auxiliary agent for dyeing bath, ink and its solvent practical system; oil-based and conversion emulsion drilling mud; gravel in dry cleaning fluid and Solid particles; particulate ceramic materials; magnetic materials and magnetic recording media, plastic materials and fungicides for flame retardants; and pesticides and pharmaceuticals used as dispersants in organic media. Preferred solids are pigments of any of the recognized pigments, as described, for example, in the third edition of the Colour Index (1971) and subsequent amendments and supplements to the title "Pigments". Examples of inorganic pigments are titanium dioxide, zinc oxide, Prussian blue, Cadmium sulfide, iron oxide, mercury sulfide, ultramarine and chromium pigments including chromic acid, salt, molybdate and mixed chromate and lead, zinc, barium, calcium sulfate and mixtures and their modifications can be named yellow , yellow, green and red pigments such as lemon, medium, orange, deep red and chrome red. Examples of organic pigments are azo, diazo, condensed azo, thioindigo, indanthrene, and isoflavone , anthrone, anthraquinone, iso-benzoxanone, triphenyl diterpene, quinophthalone and anthocyanin, especially amphetamine and its self-derivative derivatives, and acid, alkali and mordant dyes Alumina, etc. Carbon black is strictly an inorganic substance, and is more like an organic pigment in its dispersion properties. Preferred organic pigments are phthalocyanines, especially copper phthalocyanine, monoazo, diazo, and indomethacin. Lin Ketone, anthrone, quinacridone and carbon black, etc. Other preferred solids are increased Agents and fillers such as talc, kaolin, vermiculite, barite and chalk; particulate ceramic materials such as alumina, vermiculite, zirconia, titania, tantalum nitride, boron nitride, tantalum carbide, boron carbide, mixed tantalum-aluminum Nitride and metal titanate; particulate magnetic material such as magnetic oxide of transition metal, especially iron and road, such as 7*-Fe203, Fe304 and galvanic oxide, calcium oxide, ferrite, etc., especially ferric acid Salt; and metal particles, especially metal iron 'nickel, cobalt and its alloys; agricultural chemicals such as fungicides-24- This paper scale applies to China National Standard (CNS) A4 specifications (210 X 297 mm) V. Invention Description (22) flutriafen, carbendazim, chlorothalonil and mancozeb with a fire retardant such as aluminum trihydrate and magnesium hydride. The organic medium contained in the dispersant of the present invention is preferably a polar organic medium or a substantially non-polar aromatic hydrocarbon or a hydrocarbon. The term "polar" of organic media means that an organic liquid or resin can form a medium to strong bond, such as Crowley et al. in Journal of paint Techn〇1〇gy, Vol. 38, 1966, p. 269, title &quot The study of the three-dimensional space of solubility is described in the text. These organic media generally have a wind binding number of 5 or more as explained above. Examples of suitable polar organic liquids are amines, ethers, especially low alkyl ethers, organic acids, ester ketones 'diols, alcohols and decylamines. Many examples of such medium-strength hydrogen-binding liquids are listed in Ibert Mellan's title "Compatibility and Solubility"

Noyes Development, Inc.) In Table 2.14 on pages 39-40, these liquids are within the scope of the polar organic liquids used herein. Preferred polar organic liquids are dialkyl ketones, alkyl carboxylic acids and alkyl alcohols, especially such liquids containing up to and including a total of 6 carbon atoms. As examples of preferred and particularly preferred liquids, dialkyl and cycloalkyl ketones such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, decyl isobutyl ketone, diiso are described. Butyl ketone, methyl isoamyl ketone, methyl n-pentyl fluorenone and cyclohexanone; alkyl esters such as methyl acetate ethyl acetate, isopropyl acetate, butyl acetate, ethyl formate, C Methyl ester, methoxypropyl ester, and ethyl butyrate; diol and glycol esters and ethers, such as ethylene glycol, 2-ethoxyethanol, 3-methoxypropyl propanol, 夂B Oxypropyl propyl alcohol, 2-butoxyethyl acetate, acetic acid 3 - methoxy propylene, 3-ethoxypropyl acetate and 2 - ethoxyethyl acetate; alkanols such as methanol, ethanol, N-propanol, isopropanol, n-butanol and isobutanol with dialkyl ethers and cyclic ethers such as diethyl-25- paper size scale use t Η 冢 冢 standard (CNS) Α 4 specifications (210X297 dong) 1323673 A7 B7 V. Description of invention (23) Ether and tetrahydrofuran. Or a substantially non-polar organic liquid used alone or in combination with the aforementioned polar solvent. It is an aromatic hydrocarbon such as toluene and xylene, a aliphatic hydrocarbon such as hexane, heptane, octane, anthraquinone, petroleum oil such as petroleum solvent, Petroleum, vegetable oils and self-chemical aliphatic hydrocarbons such as trichloroacetic acid, perchloroethylene and chlorobenzene. As a dispersion-type mediator of the present invention, examples of suitable polar resins are film-forming resins such as those suitable for the preparation of inks, paints, and tablets for use in various applications such as paints and inks. Examples of such resins include polyamines such as VersamidTM & WolfamidTM with cellulose ethers such as ethyl cellulose and ethyl hydroxyethyl cellulose. Examples of paint resins include short oil alkyd resin/melamine-formaldehyde, polyester/melamine-formaldehyde, cooked maltoic acid/melamine-formaldehyde, strong polymeric oil alkyd, and multi-media resins such as acrylic acid and urea. /A Yue. The resin may also be an unsaturated polyester resin including so-called sheet molding compounds and bulk molding compounds which may be formulated with reinforcing fibers and fillers. Such molding compounds are available in pp. 3,643,007. ? 61*11丨113 titled "Unsaturated Polyester Skills" in the monograph, Gordon and Breach Science, 1976, 21 1-238. If necessary, the dispersant may contain other components such as a resin (when such an organic medium has not been formed), a binder, a fluidizing agent (as described in GB-A-1508576 and GB-A-2108143), and anti-deposition. Agents, toughening agents, leveling agents and preservatives. The dispersant typically contains from 5 to 95% by weight solids, depending on the nature of the solid and the relative density of the solid and organic medium. For example, the solids in the dispersant should contain 15 to 60% by weight of solids, such as organic pigments, and the dispersant in the solid -26- paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1323673 A7 B7 5. Description of the Invention (24) The body is an inorganic substance such as an inorganic pigment, and the filler or extender preferably contains 40 to 90% by weight based on the total weight of the dispersing agent. The dispersing agent is preferably prepared by grinding the solid in an organic medium at a temperature not exceeding 40 ° C, particularly not higher than 30 ° C, but if the solid is a crude phthalocyanine pigment such as copper phthalocyanine and a dispersing agent is a compound of formula 1 wherein Z It is a one-base or base-containing part, and it is sometimes preferred to grind at a temperature between 50 and 150 ° C in an organic liquid to obtain a more vivid color. The organic liquid is particularly preferred for high boiling aliphatic and/or aromatic distillates. The dispersant can be obtained by any conventional method known to prepare a dispersant. Thus, the solid, organic medium and dispersant may be mixed in any order, and the mixture is mechanically treated to reduce the solid particles to an appropriate size, such as by ball milling, bead milling, pebble milling or plastic milling until the dispersion is complete. Alternatively, the solid may be treated by mixing it alone or in combination with a convenient organic medium or dispersant to reduce its particle size, and then adding other ingredients (etc.) and stirring the mixture to prepare a dispersion. If the dry composition and the liquid medium are desired to be volatile, the particulate solid can be removed smoothly by simple separation, such as evaporation. However, the dispersion should preferably contain a liquid medium. Several compositions - consisting essentially of dispersant and particulate solids - preferably comprise at least 0.2%, preferably at least 0.5%, especially at least 1.0%, by weight of the particulate solids. Preferably, the dry composition comprises no more than 100% by weight of the particulate solids, more preferably more than 50%, more preferably no more than 20%, especially no more than 10%. As described above, the dispersant of the present invention is particularly suitable for the preparation of a grinding base in which the particulate solid is milled in the presence of both the particulate solid and the film-forming resin binder in a liquid medium. Therefore, according to still another aspect of the present invention, a grinding base is provided. Contains microparticles Solid -27- This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1323673 A7 B7 V. Description of invention (25) Body, dispersant and film-forming resin. The mill base typically comprises from 20 to 70% by weight of particulate solids based on the total weight of the mill base. Preferably, the particulate solids comprise not less than 30% by weight of the mill base, especially not less than 50%. The amount of the resin in the grinding base can vary widely, but should not be less than 10% of the continuous/liquid phase weight ratio of the grinding base, especially not less than 20%. The amount of the resin in the continuous/liquid phase of the mill base is preferably not more than 50%, particularly not more than 40%. The amount of dispersing base in the grinding base is determined by the amount of particulate solids, which is preferably 0.5 to 5% by weight of the grinding base. The dispersion and grinding base containing the dispersant of the invention are particularly suitable for paints, especially high solid paints, inks, especially letterpress intaglio and photolithographic printing inks, and non-aqueous ceramics, especially with coating, scraper 'squeezing and injection molding methods Wait. The dispersants of the present invention exhibit advantages over known dispersants derived from ε-caprolactone. It is particularly excellent in organic media such as solvents, and does not separate or crystallize when stored at 4 °C for a long period of time. Separation can occur at -24 °C during low temperature storage, but the dispersant is easily redissolved after warming to 4-1 0 °C. The incorporation of the dispersant of the present invention into paints and inks results in high gloss readings in the paints and inks produced, low haze values, low viscosity and improved flocculation properties. The invention is further exemplified by the following examples in which all relevant amounts of information are inclusive unless otherwise indicated. Intermediate of the amine dispersant The components of the POAC chain and the branched alkylene polymerization terminal group are indicated in the title of the intermediate. The number after the component in the title compound of the working example indicates the relative molar amount. For example, in Example 1, BuOcl, ε-cap 12, 5-val 2 means that 1 mol of 2-butyloctanoic acid is reacted with 12 mol ε-caprolactone and 2 mol 5-pentanolactone. -28- This paper scale applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) B7 V. Invention description (26 1ML BuOcl ' £ -cap 12 ><5 -val 2 2-butyloctanoic acid (5.0 25 mM Isocarb 12), ε-caprolactone (34_18 parts, 300 mM by Aldrich), <5-pentane vinegar (5 parts, 50 mM by Fluka) zirconium butyrate under nitrogen atmosphere 0.2 parts) in the presence of 18 ° ° (: stirred for 6 hours. After cooling, a white soft solid (44 parts) product was obtained. This was Intermediate 1, number average molecular weight Μη = 1304, polydispersity = 1.43. 6 The intermediates listed in Table 1 below were prepared in the same manner as the intermediates of Example 1, except that the molar values of the intermediates used are shown in the table. Table 1 Example intermediate alkyl terminal ε-cap 6-val Appearance Μη Pd 2 2 2 -HeDe 1 12 2 Light yellow, soft solid 1318 1.41 3 3 2-OcDo 1 12 3 Light yellow, soft solid 1873 1.47 4 4 2-DeTe 1 12 3 Light yellow, soft solid 1961 1.42 5 5 2-EtBu 1 12 3 Light yellow, solid 1681 1.46 6 6 2=EtHe 1 12 3 light yellow, solid 1538 1.53 Table 1 Footnote 2 - HeDe is 2-hexyldecanoic acid, 2-OcDo 2-octyldodecanoic acid, and 2-DeTe 2-mercaptotetradecene The acid is made by Condea, Isocarb 16, Isocarb 20 and Isocarb 24. 2-EtBu is ethyl butyrate, 2-EtHe is 2-ethylhexanoic acid, all made by Aldrich. ε-cap e-caprolactone -29- This paper scale applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 1323673 A7 B7 V. Description of invention (27) 5 -val is <5 - pentane. Μη coefficient average molecular weight.

Pd is polydisperse. Method for preparing amine dispersant

Example 7 (Bu0c 1, ε -cap 12 ' δ -val 2) PEI Intermediate 1 (44 parts, 24 mM Example 1) and polyethyleneimine (3.3 parts, 0.33 mM, Μη = 10,000 曰 触 触 触 触 触SP 200) was stirred and heated at 120 ° C for 6 hours under nitrogen. After cooling, a pale yellow product (43 parts) was obtained. This is an amine dispersion 1. The weight ratio of PEI to TPOAC acid is 1:13. Examples 8 to 12 Example 7 was repeated except that the intermediate 1 was replaced with an equivalent of the intermediate shown in Table 2. The amine dispersants listed in Table 2 all have a 1:13 PEI to TPOAC acid weight ratio. Table 2 Example amine dispersant intermediate acid appearance 8 2 2 2, HeDe 1, cap 12, val 2 brown soft solid 9 3_ 3 2-OcDo 1, cap 12, val 3 pale yellow soft solid 10 4 4 2-DeTe 1 ,cap 12, val 3 pale yellow soft solid 11 5 5 2-EtBu 1,cap 12, val 3 light yellow solid 12 6 6 2-EtHe 1,cap 12, val 3 light yellow solid Table 2 footnote TPOAC acid Explain in the footnotes in Table 1.

Example 13 13 (BuOc 1, cap 12, val 3): 1 PEI -30- This paper wave scale applies Chinese National Standard (CNS) A4 specification (210 x 297 mm) 1323673 A7 B7 V. Invention description (28) -- --- 2-butyloctanoic acid (7.31 parts, 〇·〇365Μ 'made by Condea), ε-caprolactone (50 parts, 0.438Μ 'made by Aldrich) 'valerolactone (10.96 parts, 0.11M, manufactured by Fluka) Stir at 140 ° C under a nitrogen atmosphere. Zirconium butyrate (0.3 parts, manufactured by Fluoro-Chem) was added, and the reactant was stirred at 180 to 185 ° C for 6 hours under a nitrogen atmosphere. The reaction was cooled to 9 〇 ° (: 'Addition ugly 1 (5.15 parts of SP210, MW, 20,000), and the reaction was stirred at 120-125 ° C for 6 hours under nitrogen to give a pale yellow liquid product 'cold After the formation of yellow wax (69 parts). This is the amine dispersant 7. Example 14 13 (HeDe 1, cap 12, val 3): 1 PET This was prepared in the same manner as described in Example 13, but with 2-hexyl decanoic acid (9.36 parts, 0.0365M, manufactured by Condea) as a branched acid and 5.3 parts of PEI. A yellow waxy product (72 parts), ie an amine dispersant 8. Example 1 5 13fBuOc 1 - cap! 2): l PEI 2- Butyloctanoic acid (7.31 parts, 0.0365 M, manufactured by Condea), ε-caprolactone (50 parts, 0.438 Å, manufactured by Aldrich) was stirred at 140 ° C under nitrogen. Zirconium butyrate (0.3 parts, manufactured by Fluorochem) was added, and the reactant was stirred at 180-1 85 ° C for 6 hours under a nitrogen atmosphere. The reaction was cooled to 90 ° C, PEI (4.31 parts, SP200) was added, and the reagent was stirred under nitrogen at 120-125 ° C for 6 hours. A yellow waxy product (57 parts) was obtained. That is, the amine dispersant 9. Example 16 13 (HeDe 1, cap 12): 1 PET was prepared in the same manner as described in Example 15, except that 2-hexyldecanoic acid (9.36 parts, 0.0365 m) was used as a branched alkyl group and 4.46 parts of PEI. A pale yellow waxy product (60 parts), i.e., dispersant 10, was obtained. Intermediate of acid dispersant Example 1 7 BuOc 1, cap 4, val 1 • 31 - This paper scale applies to China National Standard (CNS) A4 specification (210X 297 public)

Binding

V. INSTRUCTIONS (29) '2 Butyl Octanol (25 parts, 0.135 Μ, Isofol by Condea), e-caprolactone (61.6 parts, 0.54 Μ, manufactured by Aldrich) and α-valerolactone (13.5 parts, 〇 · 135 Μ, manufactured by BASF) heated to 12 (rc, stirred under nitrogen. Zirconium butyrate (0.25 parts, manufactured by Fluorochem), the reagent was stirred at 180_185 for 6 hours under nitrogen. After cooling, it was made into a transparent colorless oil. Substance, intermediate 7 ^ f Example 1 8 BuOc 1 , cap 5 Prepared in the same manner as described in Example 13 except that 2-butyl-indole-octanol (24 5 parts '0.132 M) and ε-caprolactone ( 75 2 parts, 〇66 μ) »After cooling, the white soft wax product, ie intermediate 8. f Example A (Pol. cap 4.4. val 1 .5) was prepared in the same manner as described in Example 13, except for dodecane Alcohol (i24.1 parts, 〇·6 Μ, manufactured by Aldrich), e-caprolactone (301 parts, 2.64 Μ, manufactured by Aldrich) and (5-valerolactone (90.1 parts, 〇·9 Μ, manufactured by Fluke) A thick oily product, intermediate A. f Example B Do 1. cap (\ Prepared in the same manner as described in Example 13 except for dodecanol (73.4 parts, 0.394 M) and έ-caprolactone ( 262.7 parts, 2.36 M). White waxy product, Intermediate Β. Acid tiller! Example 1BuOc 1, cap 4, val 1 1:1 scale intermediate 7 (50 parts, case 17) and polyphosphoric acid (5.89 parts '83% w/w ?2〇5, Manufactured under Fluke for 6 hours at 90 ° C under nitrogen to obtain a colorless oily product, ie, acid dispersant 1. f Example 20 BuOc 1. cap 5 1:1 phosphorus

1323673 A7 B7 V. INSTRUCTIONS (3〇) Prepared in the same manner as described in Example 19 except that Intermediate 8 (5 parts, manufactured by Example 14) and 5.7 parts of polylactic acid were used. It is obtained from a color waxy product, namely acid dispersant 2. I-Example Q cap 4.4. val 1 ^ ι Prepared in the same manner as described in Example 19 except that Intermediate A (partition, manufactured by Example A) and 1 〇. Obtained as a transparent oily product, ie, acid dispersant A 〇f Example D Do 1. cap6 1:1 scale was prepared in the same manner as described in Example 19 except that intermediate b (participation, example B) was used. With 1 1 · 2 parts of polyphosphoric acid. A white solid product, i.e., acid dispersant B, was obtained. Example 2 1. (QcDo 1, cap 9.5, val 3.5) 2.7:1 瑞/DEA 瞵2-octyl-1-dodecanol (50 parts, 16.7 mM, Condea, 13 〇 £ 〇 120) '£- A stirred mixture of caprolactone (18.15 parts, 159!!1]\4, 八1 (manufactured by 11^11) and α-valerolactone (5.87 parts '59 mM, manufactured by Fluka) at 140 ° C in nitrogen The mixture was mixed with butyric acid (0.2 parts, manufactured by A3CR). The reactant was further stirred under nitrogen at 180 ° C for 6 hours. The reaction was cooled to 9 Torr, and polycylinic acid (2.12 parts, 12__4 111]^ was added. 82%? 2〇5), at 90. (: The reaction was continued for 6 hours under nitrogen. The acid value of the fraction was determined to be 57.37 mg KOH/gm. The reaction reagent was cooled to 80 ° C, and diethanolamine (3.12 parts, 29.7 mM (manufactured by Fisher), the reagent was stirred at 80 ° C for 2 hours under nitrogen to obtain an orange thick liquid product which was cooled to a soft paste (26 parts). This was acid dispersant 3. Examples 22 to 31 The dispersant was made into the diethanolamine salt in the same manner as described in Example 21. Table-33- The paper scale was applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1323673 A7 B7 V. Invention Description (31) 3 Recording branched alcohols together with branched alcohols for ε-caprolactone and pentane Table 3 Example Acid dispersant Branch alcohol ε-cap δ-val TPOAC Alcohol value of the acid appearance 22 4 TDOD 9.5 3.5 52.2 Light yellow soft paste 23 5 EtHe 9.5 3.5 51.62 Light brown soft paste 24 6 TMH 9.5 3.5 60.59 Light yellow solid 25 7 DMO 9.5 3.5 54.37 Soft white paste 26 8 HE 9.5 3.5 53.48 Soft yellow solid 27 9 EB 9.5 3.5 54.01 Soft yellow solid 28 10 BuOc 9.5 3.5 49.86 Soft yellow paste 29 11 Bu/Hex 9.5 3.5 49.09 Soft yellow paste 30 12 Hex/Oct(l) 9.5 3.5 54.15 Light orange thick liquid 31 13 Hex/Oct(2) 9.5 3.5 47.01 Light yellow thick liquid Table 3 Footnote TDOD system tetradecyl stearyl alcohol ( Condea made by Isofol 32)

EtHe is 2-ethylhexanol (manufactured by Aldrich) TMH-based 3,5,5-trimethylhexanol (manufactured by Aldrich) DMO is 3,7-dimethyloctanol (manufactured by Aldrich) HE system 3-heptanol (made by Aldrich) EB is 2-ethylbutanol (made by Aldrich)

BuOc 2-but-1-octanol (Condea Isofol 12)

Bu/Hex is 2-but-1-octanol, 2-hex-1-octanol, 2-butan-1-nonanol and 2-34-- This paper scale is applicable to China National Standard (CNS) A4 specification ( 210 X 297 mm) 1323673 A7 B7 V. INSTRUCTIONS (32) A mixture of hexan-1-nonanol (Isofol 14T manufactured by Condea).

Hex/Oct(l) is 2-hex-1-enol, 2-oct-1-enol, 2-hex-1-dodecyl alcohol and 2-oct-1-butanol (Isofol 18T, Condea system)

Hex/0ct(2) is similar to Hex/Oct(l) (Isofol 1 8E, manufactured by Condea) a) Amine dispersing sword Examples 32 to 41 Solubility dissolving dispersant (2 parts) in toluene (10 ml), necessary It was warm and then checked after 16 hours at 20 °C. The samples were also stored at 4 ° C for 3 days, at -10 ° C, after 3 days, and also at -10 ° C for 3 days and then at 20 ° C for 24 hours. The results are listed in Table 4 below. The total dispersant has a ratio of TP0AC to PEI weight of 13:1. Table 4 Example amine dispersion TR0AC 24 hours at 20 ° C 3 days at 4 ° C 3 days at -10 ° C -10 ° C after 20 ° C 32 1 BuOc 1, Cap 12, val 2 transparent transparent transparent 33 2 HeDe 1, Cap 12, val 2 Transparent transparent transparent 34 3 OcDo 1, Cap 12, val 3 Transparent transparent transparent transparent 35 4 DeTe 1, Cap 12, val 3 Transparent transparent transparent transparent 36 5 EtBu 1, Cap 12, val 3 Transparent transparent transparent 37 6 EtHe 1, Cap 12, val 3 Transparent transparent transparent transparent 38 7 BuOc 1, Cap 12, val 3 Transparent transparent transparent transparent 39 8 HeDe 1, Cap 12, val 3 Transparent transparent transparent transparent -35- Ben Paper scale applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1323673 A7 B7 V. Invention description (33) 40 9 BuOc 1, Cap 12 Transparent transparent few crystal clear 41 10 HeDe 1, Cap 12 Transparent transparent Transparent Control 1 – Transparent Transparent Crystal Transparent Table 4 Footnotes Ding? 0 in (: acid is explained in Example 7-13. Control 1 is PEI and a POAC chain is derived from ε-existence according to EP 158406. Examples 42 to 51 are in 4:1 methoxypropyl acetate/n-butanol ( MPA/Bu) Solubility in the mixture. Examples 32 to 41 were repeated except that equal capacity MPA/Bu was substituted for toluene. The solubility results are listed in Table 5 below. Table 5 Example amine dispersion TROAC 24 hours at 20 ° C 3 days at 4 ° C 3 days at -10 ° C -10. After 20 ° C 42 1 BuOc 1, Cap 12, val 2 transparent transparent crystal transparent 43 2 HeDe 1, Cap 12, val 2 transparent transparent crystal transparent 44 3 OcDo 1, Cap 12, val 3 transparent transparent crystal transparent 45 4 DeTe 1, Cap 12, val 3 transparent transparent transparent transparent 46 5 EtBu 1, Cap 12, val 3 transparent and transparent. Crystal clear 47 6 EtHe 1, Cap 12, val 3 transparent transparent crystal Transparent-36- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1323673 A7 B7 V. Invention description (34) 48 7 BuOc 1, Cap 12, val 3 Transparent transparent few crystal transparent 49 8 HeDe 1, Cap 12, val 3 transparent transparent few crystal clear 50 9 BuOc 1, Cap 12 A few crystalline crystals a few crystals 51 10 HeDe 1, Cap 12 transparent few crystals crystals a few crystals of control 1 - - transparent few crystallized crystals Table 5 footnotes TPOAC and control 1 as explained in the footnote of Table 4. Examples 52 to 61 in the acetate The intrinsic solubility was repeated in Examples 32-41 except that the equivalent capacity of butyl acetate was substituted for toluene. The results are shown in Table 6. Table 6 Example amine dispersion TROAC 24 hours at 20 ° C 3 days at 4 ° C 3 days at -io °c -10°C after 20°C 52 1 BuOc 1, Cap 12, val 2 Transparent transparent few crystal clear 53 2 "HeDel, Cap 12, val 2 Transparent transparent crystal clear 54 3 OcDo 1, Cap 12, val 3 Transparent transparent few crystal clear 55 4 DeTe 1, Cap 12, val 3 transparent transparent few crystal clear 56 5 EtBu 1, Cap 12, val 3 transparent transparent crystal transparent 57 6 EtHe 1, Cap 12, val 3 transparent transparent crystal transparent -37 - This paper size applies to Chinese National Standard (CNS) A4 specification (210 x 297 mm) 1323673 A7 B7 V. Invention description (35) 58 7 BuOc 1, Cap 12, val 3 Transparent transparent few crystals. Transparent 59 8 HeDe 1, Cap 12, Val 3 transparent transparent few crystal clear 60 9 BuOc 1, Cap 12 transparent few crystalline crystals 61 10 HeDe 1, Cap 12 transparent few crystalline crystals crystallization control 1 - - transparent few crystalline crystals Table 6 footnotes TPOAC and control 1 as shown in Table 4 Explain in the footnotes. Examples 62 to 71 Pigmented decylamine dispersant A dispersion of a dissolving dispersant (〇_45 parts) in a 4:1 mixture of methoxypropyl acetate and n-butanol (7.55 parts), if necessary, was warm. Glass beads (3 mM diameter 17 parts) and red pigment (2 parts of single plastic jade red 3B, made by Avecia) were added, and the contents were ground on a horizontal shaker for 17 hours, and the fluidity of the obtained dispersion was shaken by any scale. A to E (good to bad) assessment, the results are listed in Table 7.

Table 7 Example Amine Dispersion TPOAC Fluidity 62 1 BuOc 1, cap 12, val 2 B 63 2 HeDe 1, cap 12, val 2 A/B 64 3 OcDo 1, cap 12, val 3 A/B 65 4 DeTe 1 ,cap 12, val 3 B -38- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1323673 A7 B7 V. Invention description (36) 66 5 EtBu 1,cap 12, val 3 B 67 6 EtHe 1,cap 12, val 3 C 68 7 BuOc 1, cap 12, val 3 A/B 69 8 HeDe 1,cap 12, val 3 B/C 70 9 BuOc 1,cap 12, C 71 10 HeDe 1, cap 12, B/C control 1 - - C control 2 - ~ c Table 7 footnote TPOAC and control 1 as explained in the footnote of Table 4. Control 2 is a lauric acid terminated congener of Dispersant 1, prepared as described in WO 98/19784. b) Acid dispersant Examples 72 to 7 § Solubility in toluene Examples 32 to 41 were repeated with an acid decomposing agent. The results are shown in Table 8 below. Table 8 Example Acid Dispersant TPOAC 24 hours at 20 ° C 3 days at 4 ° C 3 days at -io ° c -10 ° C after 20 ° C 72 5 EtHe 1, cap 9.5, val 3.5 Transparent transparent transparent transparent -39 - This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1323673 A7 B7 V. Invention description (37) 73 6 ΤΜΗ1, cap 9.5, val 3.5 Transparent transparent transparent 74 7 DMO 1, cap 9.5 , val 3.5 transparent transparent transparent 75 8 HE 1, cap 9.5, val 3.5 transparent transparent transparent 76 9 EB 1, cap 9.5, val 3.5 transparent transparent transparent 77 10 BuOc 1, cap 9.5, val 3.5 transparent transparent transparent 78 11 Bu/Hex 15 cap 9.5, val 3.5 Transparent transparent transparent control 3 – turbid crystal turbidity Table 8 Footnote TPOAC is explained in the footnotes of Examples 22-41 and Table 3. Control 3 is a lauric end-capped polyester phosphate ester derived from ε-caprolactone prepared as described in EP 164817. The solubility of the acid dispersants of Examples 79 to 85 in a 4:1 mixture of methyl propyl acetate / n-butanol. Example 42-5 was repeated using the following acid dispersants in Table 9. Table 9 Example Acid Dispersant TPOAC 24 hours at 20 ° C 3 days at 4 ° C 3 days at -10 ° C - 10 ° C after 20 ° C 79 5 EtHe 1, cap 9.5, val 3.5 turbid crystal falling 80 6 TMH 1, cap 9.5, val 3.5 turbid crystal: 3⁄4 /SJ 81 7 DM01, cap 9.5, val 3.5 turbid crystal / division -40 - paper scale Applicable to China National Standard (CNS) A4 specification (210X 297 mm) 1323673 A7 B7 V. Invention description (38) 82 8 HE1, cap 9.5, val 3.5 turbid crystal; SR /3⁄4] 83 9 EB 1, cap 9.5, val 3.5 turbidity/s} Crystalline 84- 10 BuOc 1, cap 9.5, val 3.5 turbid crystal 85 11 Bu/Hex 1, cap 9.5, val 3.5 turbid/SJ crystal turbidity control 3 turbid crystal crystallization crystal table 9 footnote TPOAC in example 22 -31 and Table 3 footnotes are explained. Control 3 is explained in the footnote of Table 8. f Example 86 to 92 acid dispersant dissolved in butyl acetate. Examples 52 to 61 were repeated except for the acid dispersants listed in Table 10 below: Table 10 Example Acid Dispersant TPOAC 24 hours at 20 ° C 3 days at 4 ° C 3 days at -10 ° C -lot: after 20 ° C 86 5 EtHe 1, cap 9.5, val 3.5 slightly turbid micro-turbid crystals slightly turbid 87 6 a TMH 1, cap 9.5, val 3.5 turbid crystals turbid 88 7 DMOl, cap 9.5, val 3.5 slightly turbid crystals slightly turbid 89 8 HE 1 , cap 9.5, val 3.5 turbid crystal turbidity 90 9 EB 1, cap 9.5, val 3.5 turbid crystal turbidity 91 10 BuOc 1, cap 9.5, val 3.5 turbid crystal turbidity -41 - This paper scale applies to Chinese national standards ( CNS) A4 size (210 X 297 mm) 1323673 A7 B7 V. Description of invention (39) 92 11 Bu/Hex 1, cap 9.5, val 3.5 Turbid turbidity control 3 /*j Crystalline crystallisation Table 10 Footnote TPOAC at Examples are described in the footnotes of Examples 22-31 and Table 3. Control 3 is explained in the footnote of Table 8. Examples 93 to 103 were red pigmented with an acid dispersant. The acid-decomposing agent (0.25 parts) was heated in a 4:1 mixture (6.75 parts) of methoxypropyl acetate/n-butanol, if necessary. Glass beads (3 mM, 17 parts) and red iron oxide pigment (3 parts, manufactured by Sicotrans Red L2817 BASF) were added, and the contents were ground on a horizontal shaker for 17 hours. The fluidity of the resulting dispersion was evaluated by hand shaking and using any scale A to C (good to bad). The results are listed in Table 11 below:

Table 11 Example Acid Dispersant TP0AC Flowability 93 _ 3 OcDo 1, cap 9.5, val 3.5 B 94 4 TDOD 1, cap 9.5, val 3.5 B/C 95 5 EtHe 1, cap 9.5, val 3.5 A/B 96 6 TMH 1, cap 9.5, val 3.5 B/C 97 7 DMO 1, cap 9.5, val 3.5 A 98 8 HE 1,cap 9.5, val 3.5 A -42- This paper scale applies to China National Standard (CNS) A4 specification ( 210 X 297 mm) 1323673 A7 B7 V. Description of invention (40)

99 9 EB 1,cap 9.5, val 3.5 B 100 10 BuOc 1,cap 9.5, val 3.5 B 101 11 Bu/Hex 1,cap 9.5, val 3.5 B 102 12 Hex/Oct 1,cap 9.5, val 3.5 C 103 13 Hex/Oct 1, cap 9.5, val 3.5 B Control 3 C Control 4 C Table 11 Footnote TPOAC is illustrated in the footnotes of Examples 21-31 and Table 3. Control 3 is explained in the footnote of Table 8. Control 4 is a sterol-terminated homologue of the acid dispersant 3 prepared as described in WO 98/1 9784. Examples 104 to 114 were white pigmented with an acid dispersant. Examples 93 to 103 were repeated except that 0.2 part of an acid dispersant, 2.3 parts of a solvent mixture and a white pigment (7.5 parts of titanium dioxide butadiene (16 butyl 1192, butyl hydrazine 1 (manufactured by 16 Co.)) were used. The results are shown in Table 12.

Table 12 Example Acid Dispersant TPOAC Fluidity 104 3 OcDo 1, cap 9.5, val 3.5 B -43- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1323673 A7 B7 V. Description of invention (41)

105 4 TDOD 1, cap 9.5, val 3.5 B/C 106 5 EtHe 1, cap 9.5, val 3.5 A 107 6 TMHl, cap9.5, val 3.5 B/C 108 7 DMO 1, cap 9.5, val 3.5 B/C 109 8 HE 1,cap 9.5, val 3.5 A 110 9 EB 1,cap 9.5, val 3.5 B/C 111 10 BuOc 1, cap 9.5, val 3.5 A 112 11 Bu/Hex 1? cap 9.5, val 3.5 B 113 12 Hex/Oct 1, cap 9.5, val 3.5 B 114 13 Hex/Oct 1, cap 9.5, val 3.5 A Control 3 C/D Control 4 C Table 12 Footnote TPOAC is illustrated in the footnotes of Examples 21 to 31 and Table 3. Control 3 is explained in the footnote of Table 8. Control 4 is a sterol-terminated homologue of acid dispersant 3 prepared as described in WO 98/197. Examples 115 to 125 Amine Dispersants The amine dispersants listed in Table 13 below were prepared in a similar manner as illustrated in Example 7, and the -44- paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1323673 A7 B7 V. Inventive Note (42) The TPOAC acid system was prepared in the same manner as described in Example 1. Table 1 3 indicates the preparation of the TPOAC starting material, and the description of the starting material is followed by a numerical indication of the relative molar amount. Table 13 also lists the weight ratio of TPOAC acid to amine. Table 13 also records the fluidity of a dispersion using a mixture of a single plastic jade red 3B and a 4:1 (w/w) methoxypropyl acetate/n-butanol solution according to Example 62-71. Said preparation. Table 13

Example amine dispersant TPOAC acid amine TPOAC acid to amine ratio r/w) Flowability 115 11 DeTe 1, cap8,5-Me cap 2 PEISP018 6:1 B/C 116 12 DeTe 1, cap8,5-Me cap 2 PVA 17:1 C 117 13 HeDe 1, HAS 3, cap 3 PEI SP075 10:1 B/C 118 14 BuOc 1, RA2.5 cap 2.5 PEI SP 200 14:1 B 119 15 BuOc 1, cap 10, val 2.5 PEI SP 050 11:1 A/B 120 16 HeDe 1, cap 9, 7-Me cap 3 PEI SP 030 7:1 B 121 17 One OcDo 1, cap 11 PEI SP 200 9:1 A/B 122 18 HeDe 1 ,cap 10, Gly 3 PEI SP 075 15:1 B 123 19 HeDe 1,val 12 PEI SP 050 10:1 B 124 20 BuOc 1,cap 10, val 2.5 PAA 12:1 C 125 21 3(BuOc 1, RA 2.5 cap 3.5) 9(HeDe 1,cap 9, 7-Me cap 3) PEI SP 200 12:1 B Control 1 LA 1, cap 10, val 3 PEI SP 200 18:1 C/D Control 2 SA 1, cap 3.2 Has 1.8 PEI SP 200 13:1 C/D -45- The paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1323673 A7 B7

Control 3 Cap PEI C Control 4 LA, cap, val PEI C V. Inventive Note (43) Table 13 Footnotes

DeTe 2-mercaptotetradecanoate, Isocarb 24 ° by Condea GmbH

HeDe is 2-hexyl decyl acid, Isocarb 16 manufactured by Condea GmbH. BuOc is 2-octyldodecanoic acid, Isocarb 20 manufactured by Condea GmbH. Cap is ε - the purpose of the inside, made by Aldrich.

Val Department ά - 酉 酉 ,, made by Fluka. HSA is 12-hydroxystearic acid, manufactured by Aldrich. RA is a form of onionic acid, manufactured by Aldrich. 5-Me cap is 5-methyl-ε-caprolactone, see WO 98/19784. 7-Me cap is 7-methyl-ε-caprolactone, see WO 98/19784. It is a polyethyleneimine. PVA is polyacetamide (MW 100,000), manufactured by Mitsubishi Chemical Corporation. ΡΑΑ is a polyamine base (MW 65,000), manufactured by Aldrich. SP 018 is PEI MW 1,800, Japanese catalyst type. SP 075 is PEI MW 7,500, which is a catalyst type. SP 200 series PEI MW 10,000, Japan catalyst type. SP 050 is PEI MW 50,000, Japanese catalyst type. SP 030 is a PEI MW 3,000, Japanese catalyst type. Control 1 is dispersant 22 of lauric acid 1, cap 10, glycolic acid and PEI SP 200 (18:1), WO 99/49963. -46 - This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1323673 A7 B7 V. Description of invention (44) Control 2 series stearic acid 1, cap 3.2, 12-hydroxystearic acid 1.8 and Example 4 of PEI SP 200, W0 94/21368. Control 3 is a PEI having a POAC chain derived from ε-caprolactone according to EP 158406. Control 4 is a lauric acid-terminated homolog of Dispersant 1 prepared as described in WO 98/19784. Example 126 (BuOc, cap 8, val 3 > HEA 1) PEI 7:1 2-butyloctanoic acid (1 3 parts, 0.065 M, Isocarb 12 manufactured by Condea GmbH) and sulfoxide (8.49 parts, 0.071 M, The product was made by stirring in toluene (26 ml) at 125 ° C for 8 hours to form hydrazine chloride. The toluene was removed by evaporation under reduced pressure and the residual sulphur sulphur chloride to give a brown liquid (12.6 parts). ε-Caprolactone (35 parts, 0.31 M, manufactured by Aldrich), (5-valerolactone (1 1.51 parts, 0.115 M, manufactured by Fluka), 2-hydroxyethyl acrylate (0.038 M, manufactured by Aldrich), methyl Hydroquinone (0.1 part, manufactured by Aldrich) was stirred with orthophosphoric acid (0.1 part) at 120 ° C for 8 hours under air flow. Then helium gas (8.38 parts, 0.038 m) was added, and the reactant was passed under air flow at 120 ° C. Stir for another 4 hours. The brown liquid propylene fosphate (56 parts) was obtained by cooling. The acrylate (35 parts) and ugly 13 卩 018 (5 parts, river 1 \ ¥ 1800, manufactured by Nippon Shokubai) Stirring at 65t for 2 hours gave an orange thick liquid (39 parts). This was an amine dispersant 22. The amine dispersant 22 produced a single plastic ruby 3B which exhibited fluidity B as assessed by Examples 58 to 67. Compare WO 99/ 55763 Dispersant 3 (val 3, cap 12, HEA 1 with PEI G100 (Lupasol G100, BASF, 18:1) produces flow C/D. -47- This paper scale applies to Chinese National Standard (CNS) A4 specifications (210 x 297 mm) 1323673 A7 B7 V. INSTRUCTIONS (45) Examples 127 to 138 Acid Dispersants The acid dispersants listed in Table 14 below are illustrated in the same manner as illustrated in Examples 17 and 19. Prepare only the branched alcohols and lactones indicated in the table. Identification of alcohols and lactones (etc.) followed by a number indicating the Mohr ratio. Also indicates the ratio of TPOAC alcohol to each atom in the phosphorylation agent. The fluidity of the dispersion containing Sicotrans Red L2817 and Tioxide TR 92 was also determined as described in Examples 93 to 114. Table 14 -

Example Acid Dispersant TPOAC Alcohol TPOAC Alcohol to P Ratio Amine Salt Red L2817 White TR 92 127 14 DeTe 1, cap 7, 5-Bu cap 1.5:1 . AA 128 15 OcDo 1, cap 8, 7-Me cap 3: 1 DEA B/CA/B 129 16 HeDe 1, cap 11 3:1 AA 130 17 DoHe 1, cap 7, 4-Me cap 1.5 2:1 DMEA AA 131 18* HeOc 1,cap 6, 7-Me cap 1 2.5:1 B/CB/C 132 19 CeAr 1, cap 6, 4-Me cap 3 2:1 AA 133 20 EtHe 1,cap 10, val 2.5 1.5:1 AA 134 21 Cy 1,cap 10 1.75:1 DEA AA 135 22 Nor 1,val 12 2:1 AA 136 23 CDP 1,cap 8, val 8 2.5:1 AA/B 137 24 BuOc-5EO 1, cap 6, val 2.25:1 DEA A/BA 138 25 HeDe- lOE, cap 9 2;1 AA Control 3 CC/D Control 4 CC -48- This paper wave scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1323673 A7 _______ B7 V. Invention description (46) 14 footnotes

DeTe is 2-mercapto-1-tetradecyl alcohol, which is Isofol by c〇ndea GmbH. 24 °

OcDo is 2-octyl-1-dodecyl alcohol, isofof 20 « for c〇ndea GmbH «

HeDe is 2-hexyl-1·nonanol and is Isofol 16 manufactured by c〇ndea GmbH. DoHe is 2-dodecyl-indolyl cetyl alcohol and is Isofol 28 manufactured by Condea GmbH.

HeOc is 2-hexadecyl-i-octadecanol, which is Isofol 34T manufactured by c〇ndea GmbH.

CeAr is 2-hexadecyl·ι_stanol, which is Isofol 36 manufactured by Condea GmbH.

EtHe is 2-ethylhexanol, manufactured by Aldrich.

Cy is 哀 己 hexane, made by Aldrich.

Nor is an original borneol, made by Aldrich. CDP is 3-oxo-2,2-dimethyl-1-propanol, manufactured by Aldrich.

BuOc-5ECT is 2-but-1-octanol-5EO, manufactured by Condea GmbH. HeDe-lOEO is 2-hex-1-decyl alcohol-10EO, manufactured by Condea GmbH. Cap is an internal vinegar made by Aldrich. Val is valerolactone, made by Fluka. 5-^11 cap system 5-tertene ε-caprolactone, manufactured by w〇 98/19784. 7-PCT 6 〇 &? is 7-methyl _£-caprolactone, according to '\^0 98/19784. 4-]^〇&? is 4-methyl-£-caprolactone, according to the boundary 0 98/19784. DEA is diethanolamine. -49- This paper scale applies to Chinese National Standard (CNS) Α4 specification (210X 297 mm) 1323673 A7 B7 V. Description of invention (47) DMEA is dimethylethanolamine. * Dispersant 18 is a monosulfate, and the amount of sulfuric acid shown is used instead of the phosphorylating agent (P2〇5). The phosphate of the 3 series lauryl terminated polyester was obtained from caprolactone prepared as described in EP 164817. Control 4 is the preparation of the sterol-terminated homologue of Acid Dispersant 3 as described in WO 98/19784. Examples 139 to 150 Acid Dispersants Other acid dispersants were prepared from the starting materials listed in Table 15 below using the procedures described in Examples 17 and 19. Table 15 Example Acid Dispersant TPOAC Alcohol TPOAC Alcohol to P Ratio Salt 139 26 HeDe 1, cap 3.5, val 1 1:1 140 27 OcDo 1, cap 3.2, val 0.8 1:1 141 28 HeOc 1, cap 1.95, val 0.65 1:1 142 29 HeDe 1,cap 3.2, val 1.05 1:1 143 30 BuOc 1, cap 7 1:1 144 31 BuOc 1, cap 4, val 1 1:1 145 32 HeDe 1,cap 1.75, val 0.25 1.5:1 146 33 HeDe 1,cap 4 1.25:1 147 34 HeDe 1, cap 2 1.25:1 148 35 BuOc*l, cap 6, 7-Mecap 1.5 1:1 • -50- This paper size applies to China Standard (CNS) A4 size (210X297 mm) 1323673 A7 B7 V. Description of invention (48) 149 36 OcDo 1, cap 3, 7-Mecap 1 1:1 150 37 BuOc-5EO 1, cap 3 1.375:1 Control 1 Do 1, cap 8 1:1 control 2 Do 1, cap 6, val 2 1:1 control 3 Do 1, val 3 1:1 control 4 Do 1, cap 3 2:1 袅 15 footnote

A mixture of HeDe contains 2-hexyl-1-nonanol, which is Isofol 18 butyl manufactured by Condea GmbH.

OcDo is 2-octyl-1-dodecyl alcohol, made by Condea GmbH Isofol 20 »

HeOc is a 2-hexyl decyl-octadecyl alcohol, which is made by Condea GmbH. Isofol 34T 〇

HeDe* is a mixture containing 2-hexyl-1-nonanol, which is Isofol 1 8E manufactured by Condea GmbH.

BuOc is 2-butyl-1-octanol, which is Isofol 12 manufactured by Condea GmbH.

BuOc* is a mixture of 2-butyl-1-octanol, which is Isofol 14T manufactured by Condea GmbH.

BuOc-5EO is 2-butyl-1-octanol-5 oxime, which is Isofol manufactured by Condea GmbH. Cap system ε - caprolactone, made by Aldrich. Val is <5 - pentane, made by Fluka. 7-Me cap is 7-methyl ε-caprolactone, see WO 98/19784.

Do system 1-dodecanol, manufactured by Aldrich. -51 - This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) 1323673 A7 _______B7__ V. Description of invention (49) Example 1 51 Acid dispersant (5 parts) and non-polar solvent (5 parts, Solvesso 100) is placed in an 8-dram vial and warmed as necessary to dissolve the dispersant. The samples were then stored at 4 ° C for 24 hours ' at -15. (: Stored for 48 hours, also at -15T: stored at 25 ° C for 48 hours. The results are listed in Table 16. Table 16

Acid dispersant 25 〇C 48 hours at 4 ° C 48 hours at -15 ° C 48 hours at -15 ° C after 25 ° C 26 C c HC 27 C c C c 28 Η G SO c 29 CCH c 30 c SE SO H 31 c C SE c 32 c CC c 33 c HHH 34 c CCC 35 c CHC 36 c CCC 37 c CHC Control 1 c SO SO SO Control 2 c SE SO SE Control 3 c G SO H -52- Paper scale General China National Standard (CNS) A4 Specification (210 X 297 mm) 1323673 A7 B7 V.

DESCRIPTION OF THE INVENTION (50) Control 4 C SO SO G Table 16 Footnote C is transparent, Η is turbid, G is a gel, SO is solid, and SE is seed or crystal. Controls 1 to 4 are explained in Table 15. f Example 152 Acid dispersant 26 to 37 (1.75 parts) dissolved in a non-polar liquid (1.75 parts, Solvesso 100) and added to an unsaturated poly-resin resin (50 parts) in a dispermat pressure tank externally cooled to 20 ° C , Scott-sader Crystic Resin PALV). Alumina trihydrate (87.5 parts, FRF40 made by Alcan) was added to the resin while maintaining a "rolled donut" at a higher mixing speed. When mixed for 15 minutes, the viscosity of the polyester resin form was measured at a shear rate of 250 pm using a 4 cm plate geometry on a TA instrument controlled stress flow meter. The resin forms of the acid-containing dispersants 26 to 37 showed lower viscosity and superior sedimentation resistance as compared with the known dispersants represented by the control 1-4 in Table 15. -53- This paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm). Application period ft>A. /〇 Case number 090108534 Class fly. | p丨〆〇〇卜〇(〇丨) The above columns are filled by this Council)

XT Chinese Manual Replacement Page (December 95) Chinese Dispersant Cloud! Name English dispersants Name Nationality 1. Dean Sidford DEAN THETFORD 2. Patrick John Sunderland PATRICK JOHN SUNDERLAND

3. Tom Annabo TOM ANNABLE 4 Invented #> Living, Residence, Bakerley, Hexagon House Post No. 42 tΪ^ Kerry District Hexagon House Post No. 42 • United Kingdom and Chester City Post No. 42 Name (Name) Nationality Lubrizol Corporation THE LUBRIZOL CORPORATION USA USA III. Applicant Residence, Residence (Company) Representative Name: 294, Lakeshore Road, Wickly, Ohio, USA 29400 LAKELAND BOULEVARD, WICKLIFFE, OHIO 44092-2298, USA McAfee F. This paper scale applies to China National Standard (CNS) A4 specification (210X 297 mm) 1323673 Patent application No. 090108534 Page (June 96) A7 B7 Pan·0 5:·

1L V. INSTRUCTIONS ( Ί ':}: The present invention is a novel dispersant, a dispersion containing the dispersant together with a particulate solid and a liquid mediator, a grinding substrate, and a dispersing agent and a grinding substrate in a paint, ink And plastic tread materials, including non-collision printing such as "drop-on-deman d" (DOD) printing. Dispersing agent containing a polyester chain part by one or more Hydroxycarboxylic acids or their lactone derivatives have long been known. They usually have two different chemical forms. The first type of hydroxycarboxylic acid or lactone in the presence of an alkyl carboxylic acid as a polymerization end group produces a free carboxylic acid polyester. It is then reacted with a monoamine such as polyethyleneimine. An early example of this dispersant is disclosed in EP 158 406. The second type of dispersant is polymerized in the presence of a hydroxycarboxylic acid or lactone in the presence of an aliphatic alcohol as a polymerization end group. Produced with a free acid, which is converted to cinnamic acid. An early example of this dispersing sword was announced in EP 164817. The properties of such dispersing agents such as W 〇 9 8 / 19 7 8 4 The alkyl branching of the polyester is improved, but these are not For the benefit of the use of alkyl-branched polymeric end groups. U.S. Patent 5,980,772 discloses the use of a fiber lubricant as a phosphate ester amine salt of a polyester obtained from the polymerization of ε-caprolactone and isostearic acid. The fiber lubricant inner condensed vinegar precursor is isostearyl alcohol and 1 〇 Moer e has been internalized in another fiber lubricant with 8 moles of ethylene oxide after 15 moles of ε • hex = ester reaction. Undisclosed It is found that a superior dispersant can be obtained by using a straight-like polymerization end-chain styling gel, wherein the polymerization end group contains a group of chains. According to the present invention, a dispersant of formula 1 is provided: branching fat binding

70525-960605.doc 1323673 Patent Application No. 090108534 A7 '; Chinese Manual Replacement Page (June 96) B7; < V. Description of Invention (2) Τ-Χ-(Α)η-γ-Ζ Any optionally substituted branched alkyl or cycloalkyl; hydrazine is an alkylene oxide and/or oxyalkylene; X and Y are independent divalent or direct bonds; Z is an acid or base or acid or a base moiety; and a η series of 2 to 100, including a salt thereof, a dispersant system or an isooctadecanol reacted with 1 oxime e-caprolactone or isostearyl alcohol and 8 mol epoxy B Except for the phosphate of the alkane and 15 mole ε-caprolactone reaction. Τ may be an optionally substituted aliphatic alcohol hydrazine-hydrazine residue, a randomly substituted thiol T-SH residue, a randomly substituted amine T-NHR residue, wherein r is preferably hydrogen or alkyl' Or a residue of the optionally substituted aliphatic acid T-COOH, wherein the T system is branched into an aliphatic chain or an alicyclic ring. Preferably, τ is a residue of a branched aliphatic chain which may be unsaturated but preferably saturated. Changi contains 3-50 carbon atoms, preferably 6-36 carbon, especially 6-24 carbon atoms. When substituted, the hydrazine is substituted with a cyclin' Ci-6 alkoxy group or a tertiary amino group. Preferably T is unsubstituted. What is T is the residue of the aliphatic alcohol T-OH or the residue of the aliphatic carboxylic acid T-COOH.

Examples of T-OH are isopropanol, isobutanol 'butanol, 2-ethylbutanol, 3-heptanol, 2-ethylhexanol, 3,5,5 trimethylhexanol, 3, 7-Dimethyloctanol and so-called Guerbet alcohols such as can be traded under the trade name Is〇f〇l (Condea GmbH 70525-960605.doc $ paper scale applicable to Chinese National Standards (CSS) A4 regulations (21〇Χ297 public f) 1323673

Patent Application No. 090,088,534 Chinese Manual Replacement Page (96 years 6;) V. Invention Description (3)) includes mixtures thereof. Specific examples of Guerbet alcohols are Isofol 12 ' 14T ' 16 ' 18T, 18E, 20, 24, 28, 32, 32T and 36. Examples of T_NHR are 1,5-dimethylhexylamine, t-octylamine, 2-ethylhexylamine, diisopropylamine, 2-methylbutylamine, ethylethylamine, diethylhexylamine)' 1,3- Dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane and 3-aminoheptane. T may also be a residue of an alicyclic compound such as cyclohexylamine, cyclohexyl mercaptan and cyclohexanol. Examples of T-C00H are 2-ethylbutyric acid, 2-ethylhexanoic acid, 2-butyloctanoic acid, 2-hexyldecanoic acid, 2-umyldodecanoic acid, and 2-mercapto myristic acid. Wait. This plastic knife a month acid can be obtained from Condea GmbH under the trademark Is〇earb, especially

Isocarb 12, 16, 20, 28, 32, 34T and 36. T-C00H can be a simple carboxylic acid or a mixture of such acids. Α 系 _ _ _ -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 -30 Part of the polyoxo-expanded carbonyl chain and / or polyoxo hydrazine chain, hereinafter referred to as P0AC chain. It is prepared by (co)polymerization of a hydroxycarboxylic acid or a lactone thereof. The POAC chain can be attached to the residue *τ_χ_ via a random carbonyl or oxygen atom. Τ_χ- The residue τ·χ_ is derived from the τ-Χ-sterol from the carbonyl group of the POAC chain to the end group of the polymerization reaction. Τ-Χ-linked from the oxygen atom of the POCO chain to the -Α-time residue Τ-Χ- derived from the T-X-C00H carboxylic acid as a polymerization end group. The compound produced by the (co)polymerization of monohydroxycarboxylic acid or its lactone in the presence of Τ-Χ-0Η has the formula 2 TX-0(C0-V-0)nH 2 -6- 70525-960605.doc The paper scale applies to the Chinese National Standard A4 Regulation (210 X 297 mm) 1323673 Patent Application No. 090108534 Replacement Page (June 96) A7 S61 6. 〇5 B7 V. Invention Description (4) ^ After This is called TPOAC alcohol. The compound produced by the (co)polymerization reaction of a monohydroxycarboxylic acid or a lactone thereof in the presence of T-X-COOH has the formula 3 T-X-C0(0-V-C0)n0H 3 hereinafter referred to as TPOAC acid. V in formulas 2 and 3 represents Cwo-alkylene and/or Cwo-exene. Examples of hydroxycarboxylic acids are glycolic acid, lactic acid, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, 12-hydroxystearic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxyindole Acid and 4-hydroxydecanoic acid. Suitable lactones are, for example, /5-propiolactone, optionally alkyl-substituted ε-caprolactone and optionally alkyl-substituted 5-valerolactone. The alkyl substituent in ε-caprolactone and <5-valerolactone is preferably a Chw alkyl group, particularly a Cw alkyl group, which may be a straight chain or a branched chain. The alkyl-substituted ε-caprolactone can be obtained by oxo-substituted cyclohexanone oxo reaction as described in WO 98/19784, and some are obtained as a mixture. Examples of alkyl-substituted ε-caprolactones are 7-曱, 3-曱, 5-曱, 6-, 4-, 5-tert, 4,6,6-trimethyl and 4,4,6- Tripterpene-substituted caprolactone. The alkyl-substituted -5-valerolactone is exemplified by /3 -indol-5-valerolactone. Preferred lactones are ε-caprolactone and (5-valerolactone. Preferred POAC chains are derived from ricinoleic acid, 12-hydroxystearic acid and ε-caprolactone (optional (5-valerolactone) The special POAC chain can be derived from ε-caprolactone itself or ε-caprolactone and 6-valerolactone. The molar ratio of ε-caprolactone to 5-valerolactone should be from 20:1 to 1:5, preferably from 12:1 to 1:2, more preferably from 8:1 to 1:1, especially from 5:1 to 1:1. 70525-960605.doc -7- This paper scale applies to China Standard (Ci?s) Α4 size (210 X 297 mm)

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1323673 Patent application No. 090108534 Replacement page (June 96) Contains 77狨骷5, invention description (5~~")~~""" n should not exceed 7〇' More than 50, especially not more than 20. The X-based divalent group may be a residue of a diol or a polyhydric alcohol, a dicarboxylic acid or a diisocyanate. For example, T is a residue of a monool T-OH, and a POAC residue having a terminal T-OH of A may be attached to the carboxylic acid or anhydride via a dicarboxylic acid or anhydride or a diisocyanate. Examples of the anhydride are citric acid 'adipate, phthalic anhydride and cyanoic anhydride. Suitable diisocyanates are oxime diisocyanate and hexyl diisocyanate. X-type alcohols can be a POAC chain containing carboxylic acid end groups. T-COOH is attached. Examples of suitable diols are those which can be derived from ethylene oxide and/or oxidized propylene and/or polytetrahydrofuran such as ethylene glycol and propylene glycol. The X group can also be composed of T-OH and -C2. -6-alkylene oxide, especially -C2·3·extension of a polyether obtained by the reaction of propylene oxide and/or ethylene oxide. The deuterated oxygen is preferably oxalic acid. Residue T An example of the reaction of -OH with ethylene oxide is the reaction of a Guerbet alcohol with ethylene oxide, particularly having a weight average of from 250 to 750. 'X is preferably a direct bond or a residue of a polyether" The γ-based monovalent linking group may be a residue of a di- or polyhydric alcohol, a carboxylic acid or a diisocyanate previously disclosed as X. It may also be a Z- and POAC chain when z is a base or a moiety containing a test. Times晞-type unsaturated residue. Preferred residue containing a secondary ethylenically unsaturated group comprises a -hydroxy group preferably from (deuterated) propionic acid street. Examples of compounds of each ethyl hydrazine type unsaturated group and hydroxyl group are hydroxy Ethyl (meth) propionate; acid vinegar, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyglycol _ (meth) propionate, polypropylene glycol - ( A) propylene hexanoic acid, polyglycol polytetramethylene glycol _ (meth) propionate, and polypropylene glycol polytetramethylene 70525-960605.doc · 8 -

This 尺度 尺度 scale applies Chinese national standard (C^S) A4 specification (2i 〇 X297 mm) 1323673 Patent application No. 090108534 Chinese manual replacement page (96 years 6^) V. Invention description (6~)

6. ·« - ·. ·> * - Complement (A generation) 埽 埽 ( (for example, Blemmer PE, Blemmer ΡΡ from Japan Yushi company). The ethylenically unsaturated group is preferably derived from hydroxyethyl (meth) acrylate. The Z-based acid group or the acid group-containing portion is preferably a acid ester, a sulfate ester, a phosphonate or a phosphate ester. Z is preferably a phospholipid residue. When Z is a base or a base-containing moiety, the base is preferably an amine, and the polyamine or polyimine cis-amine is ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylene. Pentaamine 'pentaethylene hexamine' N,N-dimethyl ethanediamine, pilazine, 2-methylpiperazine, 2,5-dimethylpiperazine, ^ butyl bis-amine propyl propyl Azine, N-amine ethylpiperazine, isophorone diamine, polyoxypropylenediamine, polyoxoethylenediamine, bis(4-amino-3-methyldicyclohexyl)methane, diamine Dicyclohexylmethane, bis(aminomethyl)cyclohexane, m-benzenedimethyldiamine, a-(m-aminophenyl)ethylamine, ^^(^-aminophenyl)ethylamine, m-benzene Amine, diaminodiphenylmethane, diaminodiphenyl stone and original + borneol diamine. The hydrazine may also be a residue of a substituted aliphatic tertiary amine such as 3-diamine propylamine and hydrazine, dimethyl ketamine. Examples of polyamines are polyethylamines and polyallylamines. The polyimine is preferably a poly(C2·6·extended imine), and a special polyethylenimine (hereinafter referred to as hydrazine). The polyimine may be linear or preferably branched. Linear polyethylenimine can be prepared by hydrolysis of poly(IN·醯) alkyleneimine, as described by Take 〇 Saegusa et al., MaCrom〇lecules, 1972, Vol. 5, 447 。. Branched polyethyleneimine of different molecular weights is commercially available from BASF and Nippon Shokubai. Polyallylamines of different molecular weights and poly(N-alkenyl)allylamines are commercially available from Nitto Boseki. Polyethylamines of different molecular weights are available from Mitsubishi Kasai. 70525-960605.doc This paper scale applies to Chinese national standard (C^S) A4 specification (210X297 mm)

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1323673

Patent Application No. 090108534 Replacement Page (June 96) V. INSTRUCTIONS (7) Poly(p-propylenimine) dendrimers are commercially available from DSM Fine Chemicals as poly(amidinoamine) branches. "Starburst" Branched Objects are available from Aldrich Chemical Co. The Z-based one base or the base-containing moiety is preferably a polyallylamine, a polyvinylamine-specific polyalkyleneimine such as a residue of PEI. The number average molecular weight of the polyamine or polyimine is preferably from 500 to 600,000, preferably from 1,000 to 200,000, more preferably from 1, 〇〇〇 to 1 〇〇, 〇〇〇, especially from ι, 2 〇〇. To 100,000. When Z is polyfunctional, more than one T-X-(A)n-Y- group may be attached per Z, and each segment represented by T-X-(A)n-Y may be the same or different. For example, when a z-based acid group or a residue containing an acid group such as a carboxylic acid ester is used, a dispersing agent can be obtained by reacting different TPOAC alcohols of the formula 2 with a monophosphorating agent. Similarly, when Z is a base or a moiety containing a base such as a polyamine or a polyimine (for example, PEI), one or more of the Tp〇AC acids of the formula 3 can be reacted with a polyamine or a polyimine, and the TPOAC acid can be the same. Or different from each other. In the first case of the present invention, the dispersant has Formula 1 in which the z moiety contains one base, and both χ and Υ are direct bonds. According to a first aspect of the invention, the dispersing agent comprises a polyacetamide, a polyallylamine or a poly(C2.4_alkyleneimine) having at least two P0AC chains of the formula 4 (hereinafter referred to as "PAI" ). T-C0-(0-V-C0)n. 4 where: -0-V-C0- is the part of POAC chain represented by A in formula 1; and T and η are justified as before, χ and γ of formula 1 All are direct keys. -10 - 70525-960605.doc This paper scale applies to China National Standard (Cf^s) Α4 specification (210X297 mm) 1323673 A7 B7 No. 090108534 Patent Application Chinese Manual Replacement Page (June 96) V. Invention Description (8~) Briefly, 'the type 4 POAC chain already includes oxygen and carbonyl groups indicating the attachment of the T group, and does not mean that the remaining oxygen or carbonyl group exceeds the oxygen in the alkylene group - (eighty and above. Each POAC The chain is preferably a covalent guanamine bond -CO-N< formed by a POAC chain terminal carbonyl group with a polyallylamine, a polyethylamine or a PAI inner or a secondary amine nitrogen atom, or a POAC chain terminal carbonyl group Polyallylamine, polyvinylamine or an ionic salt bond formed between a cationic nitrogen atom of a monosubstituted ammonium group in the PAI-COCTHN+e is attached to polyallylamine, polyethylamine or PAI because the dispersant contains at least two POAC chains. Therefore, the strength of the reaction conditions for the preparation method may contain a mixture of a guanamine and a salt bond. The dispersant of the first aspect of the present invention can be easily represented by the formula 5.

Wherein: Χ-'-_-Χ represents polyvinylamine, polyamphetamine or PAI; Y represents -POAC chain bonded to polyallylamine, polyethylamine or PAI via guanamine or salt; q is from 2 to 2000; and PAI and POAC are explained in the same way. q should be no less than 4, especially not less than 1〇. q should also be no more than 1 〇〇〇, preferably no more than 500. The weight ratio of POAC chain represented by Y to X---X representing polyallylamine, polyvinylamine or hydrazine is also preferably between 30:1 and 1:1, preferably between 20:1 and 5:1, special 70525 -960605.doc "u' This paper scale applies Chinese National Standard (CSS) A4 specification (210X 297 public) 1323673 Patent application No. 090108534 Replacement page (June 96) b? ... V. Description of invention (9 Between 1 7:1 and 7:1. PAI is preferably a poly(ethyleneimine), which can be linear or branched (hereinafter referred to as PEI). PAI should have a number average molecular weight from 5〇. 〇 to 600,000, preferably from 1,000 to 200,000, more preferably from 1, 〇〇〇 to 1 〇〇〇〇〇, especially from i, 2 〇〇 to 100,000 〇 Y represents POAC chain should be available from 12- Hydroxy-stearic acid, ricinoleic acid or argon-substituted ε-caprolactone or <5-lactone, including mixtures thereof. A special variant Υ can be obtained from ε-hexene of random alkane Ester and 5-valerolactone, especially from ε-Heneco and J-pentane. Another variation of the first aspect of the present invention is that the dispersant of Formula 5 contains two or more of (Y)q. Different POAC chains, depending on the dispersed particulate solids Properties and liquid media properties 'These chains may have different degrees of hydrophilicity/hydrophobicity. For example, the dispersant of formula 5 contains only two different POAC chains POAC 1 and POAC 2, and POAC 1 may be derived from one or more hydroxycarboxylic acids. At least one of which is a hydroxy-c8 3 hydrazine or a hydroxy-C8_3 () carboxylic acid, and the other hydroxy-Cl-6 alkyl carboxylic acid or a lactone thereof, and the like, and POAC 2 may be Monohydroxy-Cw stretching • The acid is derived from a mixture thereof. As a special case, p〇AC 1 can be obtained from 12-light stearic acid alone, ricinoleic acid, ricinoleic acid ε-caprolactone or 12_ Dreaming of stearic acid with ε-caprolactone, and P〇AC 2 can be obtained from ε-caprolactone alone or a mixture of ε-caprolactone and 5-valerolactone. The dispersing agent may be reacted with polyethyl s-ethylamine, polyallylamine or hydrazine with TPOAC acid of formula 4 or by polyallylamine, polyethylamine or mono- and mono-lactone (etc.) in the presence of a polymerization terminating compound.得》70525-960605.doc . ]2. This paper scales the standard of wealth (s) s) A4S) #_(21Q><297 public director)------

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1323673 Patent Application No. 090108534 Replacement Page (June 96) A7 B7 98. β· "V. Description of Invention (12) The bridge of the acid group to the POAC chain is preferably of the -KGJ type, wherein 0' S, NR or a direct bond, J system Ο, NR, a polyether or a direct bond of 1"1, alkyl, alkenyl, cycloalkyl or phenyl or its bismuth The di-R group may form a single extensor or an alkenyl group to which the attached diazogen is attached, and G is an alkylene, an alkylene, a cycloalkane or an aromatic fluorene. -K_G-J-alkyl or alkene Preferably, the group contains up to 20 carbon atoms, and the cycloalkyl group preferably contains 4 to 8 carbon atoms. The compound of formula 6 has an acidic group, and D is preferably a residue of an alcohol, a resveratrol or a primary or amine, Τ-Κ. - Ή Ή is a branched or alicyclic group. In this case Β is preferably acidic and the POAC chain has a hydroxyl end group. The hydroxyl group may contain one or more sulfates or phosphates in the dispersant. When the ester group comprises a mixture, it is esterified with a suitable sulfating or phosphating agent to obtain a monosulfate or phosphate group. Preferably, the phosphate group is preferably a phosphate esterifying agent, p2〇5, POCI3. Poly squaric acid The group represented by hydrazine or D, which is far from the acidic group, preferably contains at least 6 carbon atoms, more preferably at least 10 carbon atoms. In the second aspect of the invention, the acidic group may have a free acid form or with a base such as an amine amine, an amine group. An alcohol or an inorganic metal such as a metal or a soil-measuring metal salt is present. One of the second aspects of the present invention preferably has a dispersant of the formula 7. Τ—00(0—-V—CO)—ΟΗ (7) η Internal: Τ, V and η are interpreted as before. The second preferred dispersant of the second aspect of the invention has the general formula 8. 70525-960605.doc The paper scale is applicable to the Chinese National Standard (C^S) Α4 gauge bee ( 210X297 mm) 1323673 Patent Application No. 090108534 Replacement Page (June 96) A7 B7,-;· Supplement V, Invention Description (13)

τ—C0(0—V—CO)—D

-LM (8) wherein: L is a phosphonate, sulfonate or decylcarboxylate; hydrazine is a cation; w is 1 or 2; and Τ, V, D, η are the same as Ρ. The particularly preferred dispersant of the second aspect of the invention has the formula 9 - -J - (CO - V - 0) η • L1M (9) where: L1 is sulfate or phosphate; and T, J, V, Μ , 11 and % interpretation of the same as before. Preferably J is oxygen or a polyether. This is equivalent to the dispersant of Formula 1; wherein hydrazine is an acid group, X is a direct bond or a divalent group, and hydrazine is a direct bond. Examples of bridging groups represented by D are -NHC2H4-, -OC2H4-, 0C2H40-, -OC2H4NH-, -NH(CH2)ZNH, which are lanthanides 2 to 5, 嘻-1,4-fork and diamino-1, 4-phenyl group. A special modification of the dispersant of Formula 9 is the residue of T via a polyether, especially -16- 70525-960605.doc This paper scale applies to the Chinese National Standard (CSS) A4 specification (210 X 297 mm > 1323673 V. Patent Application No. 090108534 Replacement Page (June 96) Invention Description (14 ) A7 B7 serv:Ts

A polyethylene glycol residue is attached to the POAC chain -(CO-V-O)-. The dispersant of the second aspect of the present invention can be terminated by a POAC acid having a terminal group and a carboxylic acid group or a POAC acid (TPOAC compound) having a polymerization terminal group and a hydroxyl group or a carboxylic acid group. The acid group compound is obtained by a reaction. Alternatively, the POAC acid or TPOAC compound can be reacted directly with an acidic based precursor or with a difunctional compound which is subsequently associated with the acidic precursor. The POAC acid or TPOAC compound in the above process can be prepared in situ from a lactone (etc.) or a lactone (etc.) and a polymerization terminating compound and directly converted into a dispersing agent of the second aspect of the invention. The compound containing a suitable acid group is an amino- or α-hydroxy-alkanecarboxylic acid such as glycine and glycolic acid and an aminohydroxyorganic acid or a phosphonic acid such as an aminoethanesulfonic acid. The basicity of acidity is Ρ2Ο5 and polyphosphoric acid. Suitable difunctional compounds capable of forming a linking group between a POAC acid or a TPOAC compound and an acidic group are polyamines, polyhydric alcohols, hydroxylamines and the like. The dispersant of Formula 7 can be obtained by polymerizing a lactone (etc.) to obtain a POAC chain, and then reacting with a monocarboxylic acid T-COOH. or from a lactone (etc.) in the presence of a T-COOH as a terminal compound for polymerization. The POAC acid or its lactone (class) can be reacted with T-COOH in a suitable hydrocarbon solvent such as toluene or xylene to form an azeotropic mixture with the water produced by the esterification reaction. The reaction is preferably carried out in an inert atmosphere such as nitrogen at a temperature of 80 ° C and 25 (TC, preferably from 150 to 180 ° C. The reaction is preferably carried out in the presence of the above-mentioned monoesterification reaction. The second aspect of the invention The dispersant can also be obtained by reacting a compound of the formula 7 with a suitable co-reactant which also contains at least one acidic group and which is reactive with the carboxylic acid group of the compound of formula 7. Examples of groups which are reactive with the carboxylic acid group are amines and hydroxyl groups. Co-reaction • 17- 70525-960605.doc This paper scale applies to Chinese national standard (C^S) A4 specification (210X297 mm) 1323673 No. 090108534 patent application Chinese manual replacement page (June 96) 6. ϋ$

As an unsuitable metamorphosis, the '8 dispersant can also be obtained by reacting a unit alcohol with a preformed POAC acid and then reacting TP0AC_ with a phosphorylation or sulfation reagent. The dispersing agent of the second aspect of the present invention may contain other ester oxime or amine salt groups and the like which are formed by reacting an acid-based dispersing agent with an alcohol or an alkoxylamine. The dispersing agent of the second aspect of the present invention may be in the form of a free acid or may form a salt with an alkali heavy amine, an amine, an alkanolamine or a quaternary ammonium salt. The dispersant of the second aspect of the invention is preferably in the form of a salt with an amine. Suitable amines are for example η-butylamine, ethanolamine, aminopropanol, diethanolamine and diammonium propylamine. The dispersant of the first aspect of the invention may also be in the form of a salt with a colored acid. The term "colored acid" refers to an organic pigment or dye containing at least one acid group, preferably a sulfonic acid, a phosphoric acid or a carboxylic acid group. Preferably, the colored acid is a copper phthalocyanine or other dark pigment. The particularly sulfonated copper phthalocyanine has an average of 0.5 to 3 sulfonic acid groups per molecule. According to another aspect of the present invention, a dispersant comprising a salt thereof having one or more amine or imine groups, a POAC chain having a branched alkyl or naphthenic polymerization end group and a vinyl-unsaturated chain residue The POAC chain is bonded to the amine group and/or the imine group via an ethylenically unsaturated chain. The amine or imine group is preferably a residue of polyallylamine or polyethylamine, especially such as hydrazine. In a preferred embodiment of the invention, the dispersant has the formula 5, wherein Υ represents the remainder of the formula 13: —CH 2 —CH — C00R^"0(C0-V-0)n —OC-丁 13

I

R •21- 70525-960605.doc This paper scale applies to Chinese national standards (Ci^S) A4 regulations (210X29*7 mm) 1323673 Patent application No. 090108534 A7 Chinese manual replacement page (June 96) B7 ale:. V. Inventive Note (19) wherein R is 11 or (:1.4 alkyl; R1 is an aliphatic or aromatic residue containing up to 10 carbon atoms, optionally containing a self-propylene oxide and/or ring Oxygenethane-derived polyether residue; T, V and η are as described above.

The RgCw alkyl group is preferably a fluorenyl group. R1 is preferably C2.6 alkyl, especially C2.6 alkyl. Thus, the dispersant of the formula 1 is such that Z is a base-containing moiety and X is a direct bond 'Y-type divalent bond. A dispersant containing a chain residue of the formula 13 can be obtained by a mecogal addition reaction of a compound of the formula 14 with a monoamine, an imine, a polyamine or a polyimine. 0H2=C-COOR,-〇(CO-V-O)n OC-T 14

I

R wherein R, R1, T, V and η are as described above. The compound of formula 14 can be composed of a thiol-containing acrylic acid and optionally a pre-formed formula 3 TPOAC acid or with a T-COOH acid and one or more transbasic acid or internal vinegar at 50-150 ° C, Preferably, the reaction is preferably carried out in the presence of air or oxygen at 80-120 ° C. The reaction is preferably carried out in the presence of a catalyst such as tetraalkyl titanate such as tetrabutyl titanate, metal alkoxide such as tetraisopropyl vinegar, tin catalyst such as stannous chloride, stannous octoate or oxidized Tin, or an acid catalyst such as P-toluenesulfonic acid or trifluoroacetic acid. The reaction is also preferably carried out in the presence of a polymerization inhibitor to prevent automatic polymerization of a hydroxyl group-containing (alkene) acrylic acid. Examples of polymerization inhibitors are (meth)hydroquinolin and sulfonate. Oxygen can also be used as a polymerization inhibitor. 70525-960605.doc -22-

Claims (1)

Month A BCD 6. Patent application scope 1 · A dispersant of formula 1, TX-(A)nYZ 1 wherein the residue of the T-branched aliphatic alcohol T-OH or the residue of the branched aliphatic acid T-COOH contains 3 to 50 carbon atoms; A is an oxygen-Ci_3〇-extension base and/or oxygen-Ci_3〇-stretching base (POAC); X is a direct bond or a residue of a polyether; Y is a direct bond or a residue of a diol, a polyol, a dicarboxylic acid or a diisocyanate; z is a sulfonate, a sulfate, a phosphonate, a phosphate, a polyallylamine, a polyvinylamine or a poly(c2_6-alkylenimine); And η series 2 to 100, including the salts thereof, except that the dispersant is isostearyl alcohol and 10 mol ε-caprolactone or isostearyl alcohol with 8 mol ethylene oxide and 15 mol ε-hex Except for the phosphate ester of the lactone reaction. 2. A dispersant according to the scope of claim 1, wherein the oxime-oxime is isopropanol, isobutanol, tert-butanol, 2-ethylbutanol, 3-heptanol, 2-ethylhexanol, 3 , 5,5-tridecylhexanol, 3,7-dimethyloctanol or Guerbet alcohol, including mixtures thereof. 3. The dispersant according to claim 1 of the patent application, wherein T-COOH is 2-ethylbutyric acid, 2-ethylhexanoic acid, 2-butyloctanoic acid, 2-hexyldecanoic acid, 2-octyl-12 Alkyd or 2-decyltetradecanoic acid, including mixtures thereof. 70525-981229.doc - 1 - This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 public I) 1323673 A8 B8 C8 ________D8_ VI. Patent application scope 4. Dispersant according to the scope of patent application No. 1. Wherein a can be derived from glycolic acid, lactic acid, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, 12-hydroxyoctadecanoic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxyl Tannic acid and 4-hydroxynonanoic acid, including mixtures thereof. 5. A dispersant according to the scope of claim 1 wherein a can be derived from β-propiolactone, optionally substituted by an alkyl-substituted ε-caprolactone or, optionally, an alkyl-substituted δ-valerolactone , including its mixture. 6. The dispersant according to item 5 of the patent application, wherein the molar ratio of ε-caprolactone to δ-valerolactone is from 20:1 to 1:5. 7. The dispersant according to item 1 of the patent application, wherein η is not more than 2〇. 8. The dispersing agent according to claim 1, wherein the lanthanide is polyallylamine, polyamine or poly(Cy). 9. The dispersant according to claim 1 of the patent application, which comprises polyvinylamine, polyallylamine or poly(C2·4.alkylenimine) (PAI), which carries at least two polyoxyalkylene groups A carbonyl chain (POAC) TX-(A)nY- 〇1 分散 The dispersant according to claim 9 wherein the at least two POAC chains have different hydrophobicity/hydrophilicity. 11. The dispersing agent according to claim 10, wherein one of P〇AC is derivable from one or more hydroxycarboxylic acids, at least one of which is via a group of _Cs. -Cm-extended dilute carboxylic acid, and others are trans-alkylenecarboxylic acid or its lactone 'including mixtures thereof, and the other of p〇AC is derived from hydroxy-C!.6·alkylene carboxylate The acid or its internal vinegar, including mixtures thereof. 70525-981229.doc This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1323673 ABCD Patent Application No. 12. Dispersant according to claim 9 or 11, wherein POAC chain is for polyvinylamine, The weight ratio of polyallylamine or PAI is from 30:1 to 1:1. 13. A dispersant according to claim 1 of the scope of the patent application, wherein the X-based polyether; and the Z-based sulfate or phosphate; and mixtures thereof. 14. A dispersant according to claim 9 wherein the POAC chain residue is represented by formula 13: -CH-CH-COOR-O~(CO-Vc) n-〇CT 13 R wherein R is HSCm alkane R1 is an aliphatic or aromatic residue having up to 10 carbon atoms, optionally containing a polyether residue which may be derived from propylene oxide and/or ethylene oxide; and -(CO-VO) represents A. 15. TPOAC alcohol of the formula 2, 2 T-X-0(C0-V-0)nH wherein -(CO-V-O) represents A; and T, A, X and η are as defined in the first aspect of the patent application. 16. —TPOAC acid of formula 3, TX-C0(0-V-C0)n0H 3 70525-981229.doc This paper scale applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1323673 A8 B8 C8 D8 VI. The scope of application for patents - (0-V-CO-) stands for A; and T, A, X and η are as defined in item 1 of the scope of application. 17. - a compound of formula 14, CH2 = CH-COOR, -O(CO-VO) 〇CT 14 IR wherein R is H or (^_4 alkyl; R1 is an aliphatic or aromatic group containing up to 10 carbon atoms a family residue, optionally containing a polyether residue derivable from propylene oxide and/or ethylene oxide; -(CO-VO)- represents A; and T, A and η as claimed in claim 1 18. A method of preparing a dispersant according to claim 9 which comprises the use of TPOAC acid of formula 3 TX-C0(0-V-C0)n0H 3 wherein -(OV-CO)- Represents A; and T, A, X and η are reacted with polyvinylamine, polyallylamine or hydrazine in an inert atmosphere at 80-150 ° C as defined in the scope of claim 1 of the patent application. The method of the dispersant of claim 13 which comprises the TPOAC alcohol of the formula 2 TX-0(C0-V-0)nH 2 wherein -(CO-VO)- represents A; and T, A, X and η For example, the patent application scope is 70525-981229.doc -4- The paper scale applies to the Chinese National Standard (CNS) Α4 specification (210 X 297 mm) 1323673 ABCD VI. The scope of the patent application is defined in item 1, and the phosphorylating agent is In the inert atmosphere between 60 ° C and 120 ° C 20. A method of preparing a dispersant according to claim 14 which comprises dissolving polyvinylamine, polyallylamine or PAI with a compound of formula 14 CH2=CH-COOR-O(CO-VO) OC-T 14 I " R wherein R is an HSCm alkyl group; R1 is an aliphatic or aromatic residue containing up to 10 carbon atoms, optionally containing a polyether residue derived from propylene oxide and/or ethylene oxide - (C0-V-0)- represents A; and T, A and η are as defined in the first paragraph of the patent scope, and are reacted in an inert solvent at a temperature between 10 ° C and 130 ° C. a dispersant comprising from 5% to 95% by weight of particulate solids (based on the total weight of the dispersant), an organic medium and from 0.2% to 100% by weight of a dispersant of formula 1 as claimed in claim 1 Quantity based) TX-(A)nYZ 1 wherein the residue of the T-branched aliphatic alcohol T-OH or the residue of the branched aliphatic acid T-COOH contains 3 to 50 carbon atoms; A is milk -Ci_3〇-extension pit and/or oxygen-Ci_30_extension base; X is a direct bond or a residue of a polyether; Y is a direct bond or a diol of a diol, a polyhydric alcohol, a dicarboxylic acid or a diisocyanate 70525 -981229.doc - 5- This paper scale applies to China National Standard (CNS) A4 specification (210X 207 mm) A Be D 1323673 VI. Responsible for patent range; z is sulfonate, sulfate, phosphonate, phosphate, poly Allylamine, polyvinylamine or poly(c2.6-alkylenimine); and η from 2 to 100; including salts thereof. 22. An abrasive substrate comprising from 20% to 70% by weight of particulate solids (based on the total weight of the abrasive substrate), an organic medium, from 10% to 50% by weight of the film-forming resin and from 0.5% to 5% by weight of the patent application The formula 1 of the formula 1 dispersant Τ-Χ-(Α)η-Υ-Ζ 1 wherein the residue of the branched aliphatic alcohol oxime-ΟΗ or the residue of the branched aliphatic acid T-COOH, and Containing 3 to 50 carbon atoms; Α is oxygen-Ci_3G_ stretching group and/or oxygen-Ci_3〇- stretching group; X is a direct bond or a residue of a polyether; Y is a direct bond or a diol a residue of a polyhydric alcohol, a dicarboxylic acid or a diisocyanate; z is a sulfonate, a sulfate, a phosphonate, a phosphate, a polyallylamine, a polyvinylamine or a poly(c2.6-alkylenimine); And η series from 2 to 100; including its salts. 23. A paint comprising a ground substrate as in claim 22 of the patent application. 24. An ink comprising a grinding substrate as in claim 22 of the patent application. 70525-981229.doc -6- This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm)