WO2010143554A1 - Dispersant pour pigment et son utilisation - Google Patents

Dispersant pour pigment et son utilisation Download PDF

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Publication number
WO2010143554A1
WO2010143554A1 PCT/JP2010/059239 JP2010059239W WO2010143554A1 WO 2010143554 A1 WO2010143554 A1 WO 2010143554A1 JP 2010059239 W JP2010059239 W JP 2010059239W WO 2010143554 A1 WO2010143554 A1 WO 2010143554A1
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Prior art keywords
calcium carbonate
dispersant
meth
monomer
copolymer
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PCT/JP2010/059239
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English (en)
Japanese (ja)
Inventor
貴之 竹本
洋輔 浅井
洋一 桐戸
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東亞合成株式会社
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Priority to CN2010800248295A priority Critical patent/CN102458633A/zh
Priority to JP2011518446A priority patent/JP5776549B2/ja
Priority to SG2011072717A priority patent/SG175086A1/en
Publication of WO2010143554A1 publication Critical patent/WO2010143554A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents

Definitions

  • the present invention relates to a pigment and a dispersant for various inorganic particles. More preferably, it is a dispersing agent for calcium carbonate, and when used to produce a high-concentration pigment slurry having a solid content exceeding 70%, or particularly a pigment slurry having a small particle size, the dispersion stabilizing effect is high, and the particulate form (Meth) acrylic acid (co) can be dispersed while maintaining good fluidity, and can be stably dispersed over a long period of time while suppressing increase in slurry viscosity and pH decrease over time.
  • a dispersant for a pigment of a polymer is provided.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 54-82416
  • a pigment is dispersed with a dispersant composed of a polycarboxylic acid (salt).
  • Patent Document 2 Japanese Patent Laid-Open No.
  • a dispersant comprising a monomer containing a carboxylic acid (salt) and a copolymer of a (meth) acrylic acid ester monomer having 1 to 4 carbon atoms.
  • the pigment is dispersed.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2005-307023
  • a monomer containing a carboxylic acid (salt) and a part of terminal groups in a copolymer of other monomers are derived from an alcohol having 1 to 3 carbon atoms.
  • the pigment is dispersed with a dispersant that is a functional group.
  • a dispersant comprising a polycarboxylic acid (salt) described in Patent Document 1 or a monomer containing a carboxylic acid (salt) described in Patent Document 2 and having 1 to 4 carbon atoms (meth)
  • the dispersant composed of a copolymer with an acrylate monomer it is difficult to say that the increase in dispersion viscosity over time is sufficiently suppressed, and the inorganic pigment dispersant described in Patent Document 3
  • the resin structural unit and the neutralizing agent are not particularly optimized, and it is difficult to say that they are well suited for dispersion stabilization as an inorganic pigment dispersant, and there is no description regarding pH.
  • An object of the present invention is to provide a dispersant that is excellent in the effect of stabilizing dispersion over time of a high-concentration inorganic pigment slurry having a small particle size and the effect of suppressing the decrease in slurry pH, which is required for a dispersant in recent years, in a high pH region. It is in.
  • a dispersant having the following constitution is used for dispersing inorganic pigments, particularly calcium carbonate, despite its low pH. Surprisingly, it has been found that not only can the dispersion slurry be maintained in the strong alkali region, but also stability over time, fluidity of the slurry, and filterability are excellent, and the present invention has been achieved.
  • the second of the present invention is the pigment dispersant according to the first invention, wherein the inorganic pigment is calcium carbonate.
  • the monomer (b) unit constituting the copolymer (B) is a (meth) acrylic acid ester having 1 to 8 carbon atoms
  • the monomer (c) unit is The dispersant for calcium carbonate according to the second invention, which is a (meth) acrylic acid ester of a polyalkylene glycol represented by the general formula (I).
  • the fourth or the present invention is characterized in that the acid group in the monomer (a) unit of the polymer (A) or copolymer (B) is in the form of an organic amine salt. It is a dispersing agent for calcium carbonate as described in three inventions.
  • the fifth aspect of the present invention is a polymer (A) or copolymer (B) having a weight average molecular weight (Mw) of 4000 to 8000 by gel permeation chromatography using polyacrylic acid as a reference substance,
  • Mw weight average molecular weight
  • the sixth aspect of the present invention is the dispersant for calcium carbonate according to any one of the second to fifth aspects, which is a copolymer (B).
  • the monomer (a) unit constituting the copolymer (B) is acrylic acid
  • the monomer (b) unit is butyl acrylate
  • the monomer (c) unit is a dispersant for calcium carbonate according to any one of the second to sixth inventions, wherein R 2 in the general formula (1) is a polypropylene glycol mono (meth) acrylate having a propylene group.
  • the eighth aspect of the present invention is the dispersant for calcium carbonate according to any one of the second to seventh aspects, wherein the organic amine is monoethanolamine.
  • a ninth aspect of the present invention is a calcium carbonate dispersion having a pH of 9.5 or higher, which is prepared by wet grinding using the calcium carbonate dispersant according to any one of the second to eighth aspects.
  • the tenth aspect of the present invention is the calcium carbonate dispersion according to the ninth aspect, in which the calcium carbonate is heavy calcium carbonate.
  • the (meth) acrylic acid (salt) -based (co) polymer of the present invention is mainly used as a dispersant for inorganic pigments such as calcium carbonate, kaolin, satin white, titanium oxide, talc, calcium phosphate, cement and gypsum. Although effective, it is particularly effective when used in calcium carbonate. That is, when a calcium carbonate dispersion is prepared using a calcium carbonate dispersant comprising the (meth) acrylic acid (salt) -based (co) polymer of the present invention, the calcium carbonate concentration is high even when the calcium carbonate concentration is high.
  • the pH of the calcium carbonate dispersion can maintain a strong alkali region that can suppress bacterial growth for a long period of time. It is particularly useful because it can.
  • the dispersant for calcium carbonate of the present invention can be effectively used as a dispersion stabilizer for calcium carbonate used in the paper industry, plastics, rubber, paints, inks, adhesives, sealants, etc., taking advantage of the above-described properties. .
  • examples of the ⁇ , ⁇ -unsaturated carboxylic acid (a) include (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and citraconic acid.
  • Phthalic anhydride or itaconic anhydride may be half-esterified with alkyl alcohol. These may be used alone or in combination of two or more. Of these, preferred is (meth) acrylic acid.
  • (meth) acrylic acid means acrylic acid or methacrylic acid. More preferred is acrylic acid because of the stability of the slurry and ease of polymerization.
  • the (meth) acrylic acid ester monomer (b) of the present invention includes linear, branched and cyclic alkyl (meth) acrylates having an alkyl group of 1 to 20 carbon atoms: for example, (meth) acrylic acid Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic Examples include cyclohexyl acid and isobornyl (meth) acrylate.
  • 3-sulfopropyl (meth) acrylate mono (2-hydroxyethyl acrylate) acid phosphate, mono (2-hydroxyethyl methacrylate) acid phosphate, mono (2-hydroxypropyl acrylate) acid phosphate, mono (3-hydroxy
  • examples also include sulfonic acid and phosphoric acid group-containing (meth) acrylic acid esters such as ethyl acrylate) acid phosphate and mono (3-hydroxyethyl methacrylate) acid phosphate.
  • alkyl (meth) acrylates having 1 to 8 carbon atoms are preferred, and butyl acrylate is more preferred.
  • the monomer (c) of the (meth) acrylic acid ester of polyalkylene glycol those represented by the following general formula (1) are preferable.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an ethylene group or a propylene group
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • m represents a number of 0 to 4
  • n represents 2 to 10.
  • the molecular weight of the polyalkylene glycol chain is preferably from 100 to 2,000. More preferably, it is a polypropylene glycol mono (meth) acrylate in which R2 in the general formula (1) is a propylene group.
  • an aromatic ethylenically unsaturated monomer such as an amide-containing ethylenically unsaturated monomer: (meth) acrylamide or N-methylol (meth) acrylamide: Styrenes such as styrene, ⁇ -methylstyrene, vinyltoluene, hydroxystyrene, vinylnaphthalene and the like, sulfonic acid group-containing monomers: (meth) allylsulfonic acid, styrenesulfonic acid, ⁇ -methylstyrenesulfonic acid, isoprenesulfone Acid, vinyltoluenesulfonic acid, (meth) allyloxybenzenesulfonic acid, (meth) allyloxy-2-hydroxypropylsulfonic acid,
  • an aromatic ethylenically unsaturated monomer such as an amide-containing ethylenically unsaturated monomer: (meth) acrylamide
  • the dispersant of the present invention includes a polymer (A) comprising the monomer (a) or a copolymer comprising the monomer (a) and the monomer (b) and / or the monomer (c) ( B) can be used.
  • the copolymer (B) is preferred from the balance of calcium carbonate dispersibility, slurry stability, fluidity and filterability. In copolymer (B), when (b) and / or (c) is less than 1 mol%, the above balance is not sufficient, and when it exceeds 80 mol%, the stability in the high pH region becomes insufficient. .
  • the production method of the polymer (A) or copolymer (B) of the present invention is not particularly limited, and any of solution polymerization, emulsion polymerization, suspension polymerization and the like can be used. Of these, solution polymerization is preferred.
  • Solvents for solution polymerization include water, alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), ethers (tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, heptane, etc.), aromatic Examples include hydrocarbons (toluene, xylene, etc.) and mixtures thereof.
  • a mixed solvent of alcohol and water preferred is a mixed solvent of isopropanol and water.
  • the ratio of water exceeds 90% by mass, some of the monomers belonging to the monomer (b) and / or (c) are difficult to dissolve, which is not preferable.
  • the ratio of water is less than 10% by mass, it is not preferable because alcohol needs to be replaced with water when used as a dispersant, which is costly and labor intensive.
  • a peroxide radical polymerization initiator generally used can be used.
  • persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate
  • t-butyl hydroperoxide cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide
  • 2,5- Hydroperoxides such as dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide
  • water-soluble peroxides such as hydrogen peroxide; methyl ethyl ketone peroxide, cyclohexanone peroxide Ketone peroxides such as oxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, ⁇ ,
  • peroxide-based radical polymerization initiators may be used alone or in combination of two or more.
  • peroxide radical polymerization initiators described above hydrogen peroxide and persulfate peroxides having a low decomposition temperature that can easily control the molecular weight are more preferable.
  • the amount of the radical polymerization initiator used is not particularly limited, but is 0.10 to 15% by mass, particularly 0 based on the total mass of all monomers used for the production of the polymer (A) or the copolymer (B). It is preferably used in a proportion of 1 to 5% by mass. If the amount of radical polymerization initiator used is too small, the polymerization rate decreases, while if too large, the polymer (A) or copolymer (B) remains in the polymer (A) or copolymer (B) even after polymerization, and the stability is impaired. Or may adversely affect the performance as a dispersant.
  • a chain transfer agent may be added to the polymerization system in order to adjust the molecular weight.
  • Usable chain transfer agents include, for example, sodium phosphite, sodium hypophosphite, sodium bisulfite, mercaptoacetic acid, mercaptopropionic acetic acid, 2-propanethiol, 2-mercaptoethanol, thiophenol, dodecyl mercaptan, thio Examples thereof include glycerol and thiomalic acid.
  • the polymerization temperature for producing the polymer (A) or copolymer (B) is preferably 50 to 150 ° C, more preferably 70 to 100 ° C.
  • the polymerization temperature is lower than 50 ° C.
  • the copolymerization rate tends to decrease.
  • the polymerization temperature is higher than 150 ° C.
  • the monomer (a) causes a dimerization reaction or the monomers (b) and (c) Pyrolysis.
  • the polymerization time is preferably about 3 to 20 hours, particularly about 3 to 10 hours.
  • the above-described polymerization reaction for producing the polymer (A) or the copolymer (B) is performed at least 40 mol% or more of the acid groups of the monomer (a) before polymerization and at the polymerization stage, and more preferably 70 to 100%.
  • the polymerization is preferably carried out so that the mol%, particularly 90 to 100 mol%, is in an unneutralized state from the viewpoint that the polymerization reaction proceeds uniformly.
  • the weight average molecular weight (Mw) of the polymer (A) or copolymer (B) is usually 2,000 to 10,000.
  • the preferred range is 4,000 to 8,000.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 2.7 or less, more preferably 2.5 or less, More preferably, it is 2.4 or less.
  • Mw / Mn exceeds 2.7, the amount of low molecular weight components having low adsorptivity to calcium carbonate with time increases, and at the same time, high molecular weight components that cause the bonding (crosslinking) of calcium carbonate particles to each other. This also increases the amount of water, and as a result, it tends to cause thickening of the calcium carbonate slurry over time, which is not preferable.
  • the carboxyl group of the monomer unit (a) constituting the polymer (A) or copolymer (B) is neutralized with a basic compound to form a salt. It can be obtained by water-solubilization.
  • the basic compound used for the neutralization is ammonia or an organic amine.
  • the degree of neutralization is 20 to 80 mol%, preferably 30 to 50 mol% of the carboxyl group of the monomer unit (a) by at least one basic compound selected from ammonia or organic amine. Further, the neutralization is carried out so that 20 to 80 mol% of the carboxyl groups of the structural unit (a) are free acid groups, and thereby good dispersibility and pH with respect to the calcium carbonate slurry. It is possible to adjust a dispersant having an excellent effect of suppressing the decrease. If necessary, several kinds of ammonia and organic amines may be used, and other basic compounds may be used in combination as long as the physical properties are not impaired.
  • an aqueous solution of the polymer (A) and / or the copolymer (B), an aqueous ammonium salt solution or an organic amine salt aqueous solution of (A) and / or (B), and (A) and / or An aqueous solution obtained by neutralizing (B) with another basic compound can also be blended so as to have the neutralization ratio as described above.
  • the neutralization rate of the acid group in the (meth) acrylic acid-based (co) polymer is less than 20%, the pH immediately after the pulverization of the calcium carbonate slurry is lowered, and the pH over time as described above. This is not preferable because the effect of suppressing the decrease is weakened.
  • the basic compound used in the present invention is ammonia or an organic amine
  • the organic amine includes a primary amine, a secondary amine, and a tertiary amine.
  • the primary amine and the secondary amine for example, in the case of an aliphatic amine, a lower alkylamine having an alkyl group having 1 to 20 carbon atoms, methylamine, ethylamine, n-butylamine, octylamine, dodecylamine, dimethylamine, diethylamine, diamine, In addition to butylamine, dioctylamine, didodecylamine, etc., alkanolamines (monoethanolamine, diethanolamine, etc.), (poly) alkylenepolyamines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine), or their derivatives (alkyl) Compound, alkylene oxide adduct) and the like.
  • a tertiary amine In the case of a tertiary amine, a tertiary amine or a quaternary ammonium salt obtained by quaternizing it is included.
  • Such amines include aliphatic amines (trimethylamine, triethylamine, isopropylethylamine, octyldimethylamine, dodecyldimethylamine, etc.), alicyclic amines (N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine).
  • ammonia has a strong irritating odor, and is preferably an organic amine, more preferably an alkanolamine or a lower alkylamine.
  • Monoethanolamine is particularly preferred from the viewpoint of low odor and environmental friendliness.
  • Examples of other basic compounds that can be used in combination to neutralize the acid group in the (meth) acrylic acid (based) copolymer include alkali metal hydroxides and alkaline earth metal hydroxides.
  • alkali metal lithium, sodium, potassium and the like are preferable, and as the alkaline earth metal, calcium, magnesium, barium and the like are preferable. These may be used alone or as a mixture of two or more. Of these, sodium hydroxide is particularly preferred. However, the use of only alkali metal hydroxides or alkaline earth metal hydroxides should be avoided because the pH of the dispersion slurry decreases.
  • the dispersant of the present invention exhibits a particularly excellent effect on inorganic pigments, particularly calcium carbonate.
  • the amount of the dispersant of the present invention is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass, and particularly preferably 0.1 to 3% by mass with respect to calcium carbonate. If it is less than 0.01% by mass, the dispersion effect is insufficient, and if it exceeds 10% by mass, the dispersion tends to increase in viscosity.
  • the pH of the calcium carbonate dispersion of the present invention is preferably 8.0 or higher. If it is less than this, miscellaneous bacteria will propagate easily in a slurry, and it will become a cause of rot odor or performance will fall. More preferably, the pH is 9.5 or higher.
  • calcium carbonate used in the present invention light calcium carbonate, colloidal calcium carbonate, heavy calcium carbonate and the like are exemplified, but heavy calcium carbonate is preferable from the viewpoint of cost and the like.
  • coarse powder heavy calcium carbonate of about 400 to 40 mesh about 0.04 mm to 0.4 mm
  • the performance of the dispersant for calcium carbonate of the present invention is maximized.
  • the dispersant of the present invention exhibits an excellent effect as a dispersant for various inorganic particles such as silica particles, ceria (cerium oxide) particles, and alumina particles in addition to the above inorganic pigment dispersant.
  • silica dispersions are used in papermaking applications, metal processing applications, fiber applications, paint applications, optical material applications, and chemical mechanical polishing (hereinafter referred to as “CMP”) applications.
  • CMP chemical mechanical polishing
  • CMP is a technique used for flattening the surface of a wafer in the manufacturing process of semiconductor devices.
  • a polishing pad is attached to a polishing surface plate, the polishing pad surface is immersed in an abrasive, and the surface to be polished is pressed and pressed. In this state, the polishing surface plate is rotated, and the convex portions are removed and smoothed by mechanical friction between the abrasive and the convex portions of the object to be polished.
  • an abrasive in this CMP one obtained by dispersing silica particles or ceria particles using a dispersant is known.
  • the average particle size of the silica particles may be appropriately set according to the purpose, but is preferably 0.005 to 0.5 ⁇ m when used as a CMP abrasive. By setting the average particle size to 0.005 ⁇ m or more, when the dispersion is used in the CMP process, the polishing rate is high, and by setting the average particle size to 0.5 ⁇ m or less, sedimentation of particles can be suppressed. .
  • the blending amount of the silica particles is preferably 0.1 to 50% by weight with respect to the dispersion. By setting the content to 0.1% by weight or more, when the dispersion is used in the CMP process, the polishing rate becomes high. On the other hand, by setting the content to 50% by weight or less, aggregation of particles can be suppressed.
  • ceria dispersions are used for exhaust gas purification catalyst applications, gas sensor applications, optical material applications, and CMP applications.
  • the average particle diameter of the ceria particles may be appropriately set according to the purpose, but is preferably 0.01 to 1.0 ⁇ m when used as a CMP abrasive. By setting the average particle size to 0.01 ⁇ m or more, when the dispersion is used in the CMP process, the polishing rate is high, and by setting the average particle size to 1.0 ⁇ m or less, particle sedimentation can be suppressed. .
  • the blending amount of ceria particles is preferably 0.1 to 50% by weight with respect to the dispersion. By setting the content to 0.1% by weight or more, when the dispersion is used in the CMP process, the polishing rate becomes high. On the other hand, by setting the content to 50% by weight or less, aggregation of particles can be suppressed.
  • Alumina dispersions are used for papermaking, metal processing, textiles, paints, optical materials and ceramics.
  • a dispersant in solid content with respect to 100 parts by weight of alumina particles.
  • the average particle diameter of the alumina particles may be appropriately set according to the purpose, but is preferably 0.01 to 5.0 ⁇ m. By making the average particle diameter 0.01 ⁇ m or more, it becomes advantageous in terms of cost. On the other hand, by making it 5.0 ⁇ m or less, the ceramic becomes excellent in toughness when producing ceramic from alumina particles. .
  • the blending amount of the alumina particles is preferably 40 to 85% by weight with respect to the dispersion. By setting the content to 40% by weight or more, the ceramic can be excellent in dimensional accuracy when the ceramic is produced from the alumina particles. On the other hand, when the content is 85% by weight or less, the dispersion liquid has a low viscosity and is easy to handle.
  • the dispersion containing alumina particles obtained by using the dispersant of the present invention can be used for various applications, and can be particularly preferably used as a dispersion for producing a ceramic. In this case, it can be used together with ceramic raw material powder other than alumina.
  • ceramic raw material powder inorganic powder can be used, metal oxides such as titania, magnesia and zirconia, metal carbides such as silicon carbide, nitrides such as aluminum nitride and silicon nitride, carbonates such as calcium carbonate and barium carbonate. Examples thereof include salts and barium titanate.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the (meth) acrylic acid (co) polymer are the weight average molecular weight (Mw), the number average molecular weight (Mn), and the peak top molecular weight (Mp).
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • Mp peak top molecular weight
  • [2-d] Filterability of Heavy Calcium Carbonate Slurry Using the total amount of wet calcium pulverized slurry and alumina beads obtained by the wet pulverization treatment of [2-a] above as a sample, , Pour flatly into a cylindrical filtration apparatus (filter part is 25 cm in diameter) with a 200-mesh filter cloth, and measure the amount of filtration (g) of the slurry after 5 minutes from the start of filtration. Filterability was evaluated according to the evaluation criteria. ⁇ : 40% by mass or more of the sample passes through the filter cloth, and the filterability is extremely excellent. (Triangle
  • [2-f] pH of heavy calcium carbonate slurry The slurry with a heavy calcium carbonate concentration of 75% by mass adjusted in [2-e] above was used as a sample, and the pH value at the beginning (immediately after preparation of the sample) and after 7 days of standing was adjusted to a temperature of 25 ° C. In the state, it was measured using a pH meter (“D-12 type” manufactured by Horiba, Ltd.) and evaluated according to the following evaluation criteria.
  • ⁇ The pH value at the beginning (immediately after preparation of the sample) and after 7 days of standing are both 9.5 or more.
  • X The pH value at the beginning (immediately after preparation of the sample) and after 7 days of standing are both lower than 9.5.
  • Production Example 2 [Production of (meth) acrylic acid copolymer (B-2)] (1)
  • the same polymerization operation as in Production Example 1 (1) was carried out except that the monomer mixture was changed to 49.7 g and 44.6 g of deionized water (total 314.6 g).
  • 500 mg of the reaction solution was collected and analyzed by gas chromatography. As a result, unreacted acrylic acid and polypropylene glycol monoacrylate were not detected.
  • Production Example 3 [Production of (meth) acrylic acid polymer (A-1)] (1)
  • the monomer mixed aqueous solution was changed to a monomer aqueous solution consisting of 270.0 g of acrylic acid and 44.6 g of deionized water (314.6 g in total). Except for the above, the same polymerization operation as in (1) of B-1 was performed. After completion of the reaction, 500 mg of the reaction solution was collected and analyzed by gas chromatography. As a result, unreacted acrylic acid was not detected.
  • the average particle size of the heavy calcium carbonate particles contained in the slurry is measured by the method of [2-c] above, and the filterability of the slurry is determined. Evaluated by the above method [2-d], and further evaluated the temporal stability of the slurry by the above method [2-e], and finally evaluated the pH value of the slurry by the above method [2-f]. did.
  • the evaluation results of each example are shown in Table 1, and the evaluation results of each comparative example are shown in Table 2.
  • the viscosity on the wet pulverization day was 610 mPa ⁇ s, the viscosity after 7 days was 930 mPa ⁇ s.
  • the median diameter of the dispersion immediately after production was measured, the median diameter was 0.604 ⁇ m, and the 1.32 ⁇ under value was 98%.
  • the pH of the dispersion slurry was measured, the pH on the wet grinding day was 9.8, and the pH after 7 days was 9.8.
  • Example 2 Neutralization was performed in the same manner as in Example 1 except that the (meth) acrylic acid copolymer used in Example 1 was changed from B-1 to B-2. Thus, a pigment dispersant having a solid content concentration of 41.2% and a pH of 5.1 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 3 In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 20% monoethanolamine and 30% 48% aqueous sodium hydroxide. Thus, a pigment dispersant having a solid content concentration of 42.1% and a pH of 5.0 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 4 In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to only monoethanolamine 30%. In this way, a pigment dispersant having a solid content concentration of 42.9% and a pH of 4.4 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 5 In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 30% monoethanolamine and 50% 48% aqueous sodium hydroxide. Thus, a pigment dispersant having a solid content concentration of 41.2% and a pH of 5.9 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 6 In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to only monoethanolamine 50%. In this manner, a pigment dispersant having a solid content concentration of 43.0% and a pH of 5.2 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 7 In Example 1, neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to only monoethanolamine 80%. Thus, a pigment dispersant having a solid content concentration of 43.4% and a pH of 5.9 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 8 In Example 1, neutralization was carried out in the same manner as in Example 1 except that the neutralization rate was changed to only 50% ammonia. Thus, a pigment dispersant having a solid content concentration of 40% and a pH of 4.9 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 9 Neutralization was performed in the same manner as in Example 1 except that the (meth) acrylic acid-based (co) polymer used in Example 1 was changed from B-1 to A-1. In this manner, a pigment dispersant having a solid content concentration of 42.3% and a pH of 5.1 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 1 neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 97% neutralization with a 48% sodium hydroxide aqueous solution. Thus, a pigment dispersant having a solid content concentration of 40% and a pH of 8.0 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 2 Neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 30% with monoethanolamine and 67% with 48% sodium hydroxide aqueous solution. In this way, a pigment dispersant having a solid content concentration of 40.7% and a pH of 8.1 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 3 neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 50% neutralization with a 48% sodium hydroxide aqueous solution. Thus, a pigment dispersant having a solid content concentration of 40.5% and a pH of 5.1 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 4 neutralization was performed in the same manner as in Example 1 except that the neutralization rate was changed to 97.0% neutralization with monoethanolamine. In this manner, a pigment dispersant having a solid content concentration of 43.2% and a pH of 8.2 was obtained. Using this neutralized polymer, wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • Example 5 Comparative Example 5
  • the (meth) acrylic acid (co) polymer used was changed from B-1 to A-1, and the neutralization rate was 30% with monoethanolamine and 67% with 48% aqueous sodium hydroxide.
  • % Neutralization was carried out in the same manner as in Example 1 except that the amount was changed to neutralize.
  • a pigment dispersant having a solid content concentration of 39.9% and a pH of 8.0 was obtained.
  • wet calcium carbonate was wet pulverized by the method described in [2-a] above, and each dispersion characteristic of the dispersion slurry was evaluated.
  • the dispersing agent for calcium carbonate useful for the dispersing agent for inorganic pigments especially a high concentration pigment slurry, and a pigment slurry with a small particle diameter
  • the dispersion pigment has a high stabilizing effect and can be dispersed while maintaining good fluidity in the form of fine particles, so that the viscosity and pH of the slurry over time can be increased over a long period of time.
  • a stable dispersion is obtained.
  • the dispersion is optimal for the paper industry, plastics, rubber, paints, inks, adhesives, sealants and the like.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention porte sur un dispersant pour pigments composé de (co)polymères d'acide (méth)acrylique ou un dispersant pour diverses particules inorganiques, qui a un effet de stabilisation de la dispersion élevée et qui est apte à disperser de façon stable des pigments et diverses particules inorganiques pendant longtemps, tout en évitant une augmentation de viscosité ou une diminution de pH de suspension épaisse de celui-ci au cours du temps et en maintenant donc une bonne fluidité de la suspension épaisse. Une suspension épaisse classique d'un pigment inorganique qui comporte des particules de petite taille est susceptible d'avoir une viscosité de suspension épaisse accrue dans la mesure où l'interaction entre les particules est forte du fait des surfaces accrues, et provoque ainsi l'agrégation des particules. De façon spécifique, l'invention porte sur un dispersant pour un pigment qui est composé d'un produit partiellement neutralisé de (A) un polymère de (a) un monomère acide carboxylique α,β-insaturé ou (B) un copolymère qui est composé de 80-99 % en moles d'un motif de (a) le monomère acide carboxylique α,β-insaturé et 1-20 % en moles d'un autre motif qui composé de (b) un monomère ester (méth)acrylate et/ou (c) un monomère ester (méth)acrylate d'un polyalkylène glycol ((a) + (b) + (c) représentant 100 % en moles). Le dispersant pour un pigment est caractérisé en ce que de l'ammoniac ou une amine organique est utilisée comme agent neutralisant.
PCT/JP2010/059239 2009-06-11 2010-06-01 Dispersant pour pigment et son utilisation WO2010143554A1 (fr)

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JP2011006621A (ja) * 2009-06-29 2011-01-13 San Nopco Ltd 無機粒子スラリー用流動性改良剤
JP2011256225A (ja) * 2010-06-07 2011-12-22 Nippon Shokubai Co Ltd ポリ（メタ）アクリル酸系重合体水溶液およびその製造方法
JP2013518160A (ja) * 2010-01-27 2013-05-20 オムヤ・デイベロツプメント・アー・ゲー 炭酸カルシウム含有物質の水性懸濁液における添加剤としてのポリエチレンイミンの使用
JP2013533336A (ja) * 2010-06-07 2013-08-22 オムヤ・デイベロツプメント・アー・ゲー 炭酸カルシウム含有材料の水性懸濁液中の添加剤としての２−アミノエタノールの使用
JP2014105222A (ja) * 2012-11-22 2014-06-09 San Nopco Ltd 減粘剤、排ガス浄化触媒用スラリー及びこの製造方法、並びに内燃機関
JP2015511207A (ja) * 2011-12-22 2015-04-16 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 炭酸カルシウムスラリー
JP2015150530A (ja) * 2014-02-18 2015-08-24 株式会社日本触媒 無機微粒子分散剤
JP5873009B2 (ja) * 2010-04-07 2016-03-01 株式会社日本触媒 ポリ（メタ）アクリル酸系重合体水溶液およびその製造方法
US9777090B2 (en) 2010-10-29 2017-10-03 Bellandtechnology Ag Water-soluble or water-disintegrable copolymer
WO2018081964A1 (fr) * 2016-11-02 2018-05-11 Basf Se Polymères d'acide acrylique neutralisés par des ions sodium et calcium et présentant une étroite distribution des masses moléculaires
JP2018512492A (ja) * 2015-04-10 2018-05-17 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 装飾セラミック市場用の修飾されたポリアクリレート分散剤
CN116003680A (zh) * 2022-12-26 2023-04-25 天集化工助剂（沧州）有限公司 一种聚合型抗光老型多功能添加剂及其制备方法和应用

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CN105777973B (zh) * 2016-03-04 2018-01-12 山东德胜精细化工研究院有限公司 一种两亲共聚物分散剂、制备方法及应用
JP6704151B1 (ja) * 2019-04-15 2020-06-03 株式会社Ｔｂｍ 無機物質粉末充填樹脂組成物、及び成形体

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011006621A (ja) * 2009-06-29 2011-01-13 San Nopco Ltd 無機粒子スラリー用流動性改良剤
JP2013518160A (ja) * 2010-01-27 2013-05-20 オムヤ・デイベロツプメント・アー・ゲー 炭酸カルシウム含有物質の水性懸濁液における添加剤としてのポリエチレンイミンの使用
JP5873009B2 (ja) * 2010-04-07 2016-03-01 株式会社日本触媒 ポリ（メタ）アクリル酸系重合体水溶液およびその製造方法
JP2016117906A (ja) * 2010-04-07 2016-06-30 株式会社日本触媒 ポリ（メタ）アクリル酸系重合体水溶液およびその製造方法
JP2011256225A (ja) * 2010-06-07 2011-12-22 Nippon Shokubai Co Ltd ポリ（メタ）アクリル酸系重合体水溶液およびその製造方法
JP2013533336A (ja) * 2010-06-07 2013-08-22 オムヤ・デイベロツプメント・アー・ゲー 炭酸カルシウム含有材料の水性懸濁液中の添加剤としての２−アミノエタノールの使用
US10308743B2 (en) 2010-10-29 2019-06-04 Bellandtechnology Ag Water-soluble or water-disintegrable copolymer
US9777090B2 (en) 2010-10-29 2017-10-03 Bellandtechnology Ag Water-soluble or water-disintegrable copolymer
JP2015511207A (ja) * 2011-12-22 2015-04-16 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 炭酸カルシウムスラリー
JP2014105222A (ja) * 2012-11-22 2014-06-09 San Nopco Ltd 減粘剤、排ガス浄化触媒用スラリー及びこの製造方法、並びに内燃機関
JP2015150530A (ja) * 2014-02-18 2015-08-24 株式会社日本触媒 無機微粒子分散剤
JP2018512492A (ja) * 2015-04-10 2018-05-17 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 装飾セラミック市場用の修飾されたポリアクリレート分散剤
JP2022003151A (ja) * 2015-04-10 2022-01-11 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 装飾セラミック市場用の修飾されたポリアクリレート分散剤
JP7416743B2 (ja) 2015-04-10 2024-01-17 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 装飾セラミック市場用の修飾されたポリアクリレート分散剤
WO2018081964A1 (fr) * 2016-11-02 2018-05-11 Basf Se Polymères d'acide acrylique neutralisés par des ions sodium et calcium et présentant une étroite distribution des masses moléculaires
CN116003680A (zh) * 2022-12-26 2023-04-25 天集化工助剂（沧州）有限公司 一种聚合型抗光老型多功能添加剂及其制备方法和应用

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