WO2007110920A1 - Silice hydrophobe - Google Patents

Silice hydrophobe Download PDF

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Publication number
WO2007110920A1
WO2007110920A1 PCT/JP2006/306224 JP2006306224W WO2007110920A1 WO 2007110920 A1 WO2007110920 A1 WO 2007110920A1 JP 2006306224 W JP2006306224 W JP 2006306224W WO 2007110920 A1 WO2007110920 A1 WO 2007110920A1
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WO
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Prior art keywords
group
silica
carbon atoms
hydrophobic silica
diisocyanate
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PCT/JP2006/306224
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English (en)
Japanese (ja)
Inventor
Chonghui Wang
Tadakazu Motohashi
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Hakuto Co., Ltd.
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Priority to PCT/JP2006/306224 priority Critical patent/WO2007110920A1/fr
Priority to JP2008507308A priority patent/JPWO2007110920A1/ja
Publication of WO2007110920A1 publication Critical patent/WO2007110920A1/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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3081—Treatment with organo-silicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/3063—Treatment with low-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081

Definitions

  • the present invention relates to hydrophobic silica used in paints, rubbers, resins, agricultural chemicals, papers and the like.
  • Hydrophobic silica has made use of its hydrophobicity, and has traditionally been used as a general paint matting agent, photoaging inhibitor, water-proofing agent, oil-proofing agent, chemical-proofing agent and filler, ship bottom Antifouling additives for paint stains (shells), surface slipperiness improvers for rubber and resin, wear resistance improvers and mechanical strength reinforcing agents, fluidization of fine powders such as toner for electrostatic copying machines
  • Hydrophobic silica is mainly used to make hydrophobic silica, which is used as a carrier for hydrophobic components of chemicals, pesticides, antifoam components, water repellents, oil repellents, and blocking agents for paper.
  • Various methods have been proposed in the past.
  • a method of obtaining hydrophobic silica by reacting hydrophilic silica with methylchlorosilane or silane coupling agent a method of hydrophobizing with hydrophilic silica and high molecular weight organopolysiloxane, hexamethyldisilazane (HMDS) And a method of hydrophobizing with onoreganopolysiloxane (for example, see Patent Document 1).
  • the ability to easily obtain hydrophobic silica by these methods The modified hydrophobicity of the hydrophobic silica (see Patent Document 2) is limited to around 70%.
  • silane-powered primer and / or organopolysiloxane is only attached to the surface of the silica where it reacts with the silica surface.
  • separation of silane coupling agent from hydrophilic silica and Z or onoleganopolysiloxane occurs depending on the use environment.
  • hydrophilic silica surface treatment of hydrophilic silica with polyethylene wax is used as an exuding agent for paints (see, for example, Patent Document 3), and hydrophilic silica is basic such as water vapor and ammonia
  • H MDS hexamethyldisilazane
  • Patent Document 1 JP-A-5-97423
  • Patent Document 2 JP-A-8-259216
  • Patent Document 3 Japanese Patent Laid-Open No. 7-166091
  • Patent Document 4 JP-A-8-259216
  • the purpose of the present invention is to improve the photo-aging prevention performance of general paints, improve water resistance and oil resistance, improve the dirt (shell) adhesion prevention performance of ship bottom paint, and improve the surface slipperiness of rubber and resin.
  • hydrophilic silica after reacting hydrophilic silica and an aminoalkylsilane compound to introduce a reactive amino group on the surface of the hydrophilic silica, the amino group is further reacted with a specific compound.
  • the resulting hydrophobic silica has high hydrophobicity.
  • the invention according to claim 1 is characterized in that the hydrophilic silica is represented by the general formula (1) (wherein R 2 is independently an alkylene group having 1 to 4 carbon atoms, R 3 , R 5 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and n is an integer of 0 to 5.
  • R 2 is independently an alkylene group having 1 to 4 carbon atoms
  • R 3 , R 5 is independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms
  • n is an integer of 0 to 5.
  • an aminoalkylsilane compound represented by general formula (2) (wherein R 6 is a linear or branched alkyl group having 2 to 21 carbon atoms, and having 2 to 21 carbon atoms) A carboxylic acid compound represented by a straight or branched alkenyl group, X is a hydroxyl group, a chlorine atom, or a bromine atom), general formula (3) (wherein R 8 is a straight chain having 1 to 20 carbon atoms) Chain or branched chain An alkyl group, a linear or branched alkenyl group having 1 to 21 carbon atoms, and an alkylphenyl group having 6 to 24 carbon atoms.
  • Alkylketene dimer represented by general formula (4) (wherein R 9 is an alkylene group having 6 to 24 carbon atoms and an alkylphenylene group having 6 to 24 carbon atoms). It is a hydrophobic silica obtained by reacting with a hydrophobizing agent containing one or more selected from cyanate compounds.
  • the invention according to claim 2 is the hydrophobic silica according to claim 1, wherein the aminoalkylsilane compound is 2-aminoethyltriethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) _ It is characterized by being one or more of 3-aminopropyltrimethoxysilane.
  • the invention according to claim 3 is the hydrophobic silica according to claim 1, wherein the hydrophobizing agent is decanoic acid, dodecanoic acid, stearic acid, decanoic acid chloride, dodecanoic acid chloride, stearic acid salt Hardened beef tallow alkyl (carbon number 14-18) ketene dimer, stearyl ketene dimer, beninole ketene dimer, 1,6-hexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate, It is one or more of xylylene diisocyanate and tolylene diisocyanate.
  • the hydrophobizing agent is decanoic acid, dodecanoic acid, stearic acid, decanoic acid chloride, dodecanoic acid chloride, stearic acid salt
  • the invention according to claim 4 is the hydrophobic silica according to any one of claims 1 to 3, wherein the hydrophilic silica is treated with an aminoalkylsilane compound and then the hydrophobizing agent in the presence of a fluorosurfactant. Hydrophilic silica treated with an aminoalkylsilane compound is hydrophobized by the above.
  • the hydrophobic silica of the present invention can obtain a higher water repellency than the hydrophobic silica produced by the conventional method, and can improve the anti-aging property and water resistance * oil resistance of general paints. Improves dirt (shell) adhesion prevention performance on ship bottom paint, improves surface slipperiness of rubber and resin, improves wear resistance and mechanical strength, improves fluidity of toner in electrostatic copier, It is possible to greatly contribute to improving the defoaming performance of the foaming agent and the blocking performance of the paper.
  • hydrophilic silica and an aminoalkylsilane compound are reacted to introduce a hydrophobic group having a reactive amino group on the surface of the hydrophilic silica, and then the amino group and It is a hydrophobic silica having a high hydrophobicity obtained by reacting with one or more hydrophobizing agents selected from certain carboxylic acid compounds, alkyl ketene dimers or alkenyl ketene dimers, and diisocyanate compounds.
  • hydrophilic silica used in the present invention is not particularly limited, and may be any of wet precipitation silica, wet gel silica, dry silica (including fumed silica produced by flame pyrolysis of chlorosilane), etc. These silicas may be used alone or in combination.
  • the aminoaminosilane compound used in the present invention is an aminoaminosilane compound represented by the general formula (1).
  • R 2 is an alkylene group having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, isopropylene group, butylene. A len group and an isobutylene group.
  • R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, such as a hydrogen atom, a methyl group, an ethyl group, or a propyl group.
  • Specific aminoalkylsilane compounds include 2_aminoethyltrimethoxysilane, 2_aminoethyltriethoxysilane, 2-aminoethylethylethyloxysilane, 3-aminopropyltriethoxysilane, N- (2- Aminoethyl) 1-2-aminoethyltriethoxysilane, N- (2-aminoethyl) 1-2-aminoethylethylethyloxysilane, N- (2-aminoethyl) _3-aminopropylmethyldimethoxysilane, N— (2-aminoethyl) 1-3-aminopropyltrimethoxysilane, N— (2-aminoethyl) 1-3-
  • the reaction between the hydrophilic silica and the aminoalkylsilane compound is not particularly limited and is performed according to a normal hydrophobizing reaction.
  • the amount of aminoalkylsilane compound used can be calculated according to the following formula.
  • the minimum coverage is calculated from the Stuart-Briegleb molecular model.
  • the amount of aminoalkylsilane compound used is appropriately selected depending on the intended use of hydrophobic silica and the degree of hydrophobicity required, and is usually 2 to 20 wt% with respect to hydrophilic silica.
  • aminoalkylsilane compound used is 2wt of silica.
  • the hydrophobization rate of the hydrophilic silica may be low, and the degree of hydrophobization of the produced hydrophobic silica may not be sufficiently high, which may be undesirable.
  • Aminoa If the amount of the alkylsilan compound used is 20 wt% or more of the hydrophilic silica, the cost of the aminoalkylsilane compound used is high and uneconomical, and the produced hydrophobic silica tends to aggregate, resulting in dry dispersion. It may be difficult to do so and may not be preferable.
  • the aminoalkylsilane compound is used as it is, a method of using an aminoalkylsilane compound as it is, a method of preparing and using a dilute aqueous solution having a concentration of 0.5 to 2 wt%, and a solution in a water-soluble organic solvent. And a method of dissolving and using in a water-insoluble organic solvent, and any method may be used.
  • the method of adding the aminoalkylsilane compound to the hydrophilic silica is not particularly limited.
  • the mixer is mixed with the hydrophilic silica in a blender, and the aminoalkylsilane compound is directly added while stirring.
  • there is a method of spray-coating an aqueous solution of an aminoalkylsilane compound or a diluted organic solvent, and any of them may be used.
  • reaction time between the hydrophilic silica and the aminoalkylsilane compound is appropriately selected depending on the intended use of the hydrophobic silica force and the required level of hydrophobicity, and cannot be determined uniformly, but is usually preferably 5 to 100 minutes.
  • the reaction proceeds almost completely in 20 to 60 minutes, and the aminoalkylsilane compound reacts with the OH group on the hydrophilic silica surface with the reactive amino group facing outward and binds.
  • the carboxylic acid compound used in the hydrophobizing agent of the present invention is a carboxylic acid or a carboxylic acid halide represented by the general formula (2).
  • R 6 in the general formula (2) is a linear or branched alkyl group having 2 to 21 carbon atoms or a linear or branched alkenyl group having 2 to 21 carbon atoms, and X is a hydroxyl group or a chlorine atom. A bromine atom.
  • carboxylic acid examples include propionic acid, butanoic acid, hexanoic acid, decanoic acid, dodecanoic acid, myristic acid, isomyristic acid, palmitic acid, isopalmitic acid, stearic acid, isostearic acid, oleic acid, 1 2-hydroxystearic acid, behenylic acid and the like.
  • carboxylic acid halide having 3 to 22 carbon atoms include acid chlorides and acid bromides of the above carboxylic acids. Specifically, propionate chloride, propionate bromide, butanoic acid chloride, and hexanoic acid.
  • Chloride decanoic acid chloride, dodecanoic acid chloride, myristic acid chloride, isomyristic acid chloride, palmitic acid chloride, isopalmitic acid chloride, stearic acid salt, stearic acid bromide Products, isostearic acid chloride, isostearic acid bromide, oleic acid chloride, 12-hydroxystearic acid chloride, behenyl acid chloride and the like. These can be used alone or in combination of two or more.
  • the alkyl ketene dimer used in the hydrophobizing agent of the present invention is an alkyl ketene dimer represented by the general formula (3).
  • R 7 and R 8 are each a straight chain or branched chain alkyl group, alkenyl group, or alkylphenyl group having carbon numbers:! -20.
  • alkyl ketene dimers include propylene ketene dimer, butylene ketene dimer, octyl ketene dimer, 2-ethyl hexyl ketene dimer, decyl ketene dimer, dodecyl ketene dimer, coco alkyl (10 to 12 carbon atoms) ketene dimer, Tetradecyl ketene dimer, hexadecyl ketene dimer, stearyl ketene dimer, isostearino ketene dimer, vinyl ketene dimer, cured beef tallow alkyl (carbon number 14-18) ketene dimer, tallow alkyl (carbon number 14-18) ) Ketene dimer, oleyl ketene dimer, butyl phenyl ketene dimer, octyl phenyl ketene dimer, nonyl phenyl keten
  • Alkyl (8-18 carbon atoms) ketene dimer (AKD). These can be used alone or in combination of two or more. An alkyl ketene dimer having less than 10 carbon atoms may not be sufficiently hydrophobized, and an alkyl ketene dimer having more than 48 carbon atoms may be difficult to obtain industrially.
  • the diisocyanate compound used in the hydrophobizing agent of the present invention is a diisocyanate compound represented by the general formula (4).
  • R 9 is an alkylene group having 6 to 24 carbon atoms or an alkylphenylene group having 6 to 24 carbon atoms.
  • 1,6-hexamethylene diisocyanate, 2, 2, 4_trimethyltetramethylene of alkylene disiocyanates 1,6-hexamethylene diisocyanate, 2, 2, 4_trimethyltetramethylene of alkylene disiocyanates.
  • decanoic acid, dodecanoic acid, stearic acid, decanoic acid chloride, dodecanoic acid chloride, stearic acid chloride, and cured beef tallow alkyl (carbon number 14 to 18) ketene are preferred as hydrophobizing agents.
  • stearic acid chloride, stearyl ketene dimer, and tolylene diisocyanate are more preferable. These can be used alone or in combination of two or more.
  • dimethylpolysiloxane a dimethylpolysiloxane having a terminal reactive hydroxyl group
  • hydrogenmethylpolysiloxane trimethylchlorosilane which has been conventionally used as long as it does not interfere with the effects of the present invention.
  • a silane coupling agent such as
  • the mixing ratio of the hydrophilic silica treated with the hydrophobizing agent and the aminoalkylsilane compound is determined based on the carboxylic acid compound, alkyl ketene dimer, diisocyanate compound that is the hydrophobizing agent.
  • the ratio of the total number of moles of reactive functional groups to the number of moles of reactive amino groups in the aminoalkyl silane compound is 1 ::! To 2: 1, preferably 1.1: 1 to 1: 1.5: 1 It is.
  • the number of moles of reactive functional groups per mole of carboxylic acid compound, alkyl ketene dimer, and diisocyanate compound is 1 mole for carboxylic acid compounds, 1 mole for alkyl ketene dimers, and diisocyanate. For compounds, it is 2 moles.
  • Molar ratio power of reactive amino groups in aminoalkylsilane compounds Range of the ratio If it is smaller than 1, sufficient hydrophobicity cannot be obtained due to the amino group remaining in the reaction. In addition, even if the total number of moles of the hydrophobizing agent exceeds the range of the ratio, there is no economic merit that the hydrophobicity cannot be improved enough to meet the increase.
  • the method of using the hydrophobizing agent includes the method of using the hydrophobizing agent as it is, the method of using the hydrophobizing agent as a solution by dissolving it in an organic solvent or water-soluble organic solvent having a concentration of! Any method may be used.
  • organic solvents or water-soluble organic solvents include toluene, xylene, methyl ethyl ketone, and butyl cellosolve.
  • the method for adding the hydrophobizing agent is not particularly limited. Usually, a method is used in which a hydrophilic silica treated with an aminoalkylsilane compound is placed in a mixer or a blender, and the hydrophobizing agent is directly added while stirring, or There is a method of spraying a solvent dilution of a hydrophobizing agent, and any method may be used.
  • reaction time between the hydrophobizing agent and the hydrophilic silica treated with the aminoalkylsilane compound is appropriately selected depending on the intended use of the hydrophobic silica and the degree of hydrophobicity, but cannot be determined uniformly. ⁇ : 120 minutes, preferably 30 to 90 minutes.
  • hydrophobic silica with excellent dispersibility can be obtained by adding a fluorosurfactant during the hydrophobization reaction between the hydrophobizing agent and hydrophilic silica treated with an aminoalkylsilane compound.
  • fluorine-based surfactant to be added there are fluorine-based compounds represented by the general formulas (5) to (7).
  • R 1Q is a perfluoroalkyl group having 5 to 22 carbon atoms
  • X is COM
  • SO M group M is Na, K, L
  • R 11 is a perfluoroalkyl group having 5 to 22 carbon atoms
  • Y is H (hydrogen atom)
  • -OPO (OH) phosphoric acid residue
  • p is an integer of:! To 15 It is.
  • R 12 is a perfluoroalkyl group having 5 to 22 carbon atoms
  • Z is a chlorine atom, bromine atom, iodine atom, sulfuric acid residue, phosphoric acid residue, or a carboxylic acid residue having 1 to 6 carbon atoms.
  • the number of carbon atoms is 4 or less, the surface tension of the fluorine compound is low and it volatilizes, making it difficult to handle immediately. In addition, when the number of carbon atoms exceeds 22, it becomes difficult to obtain industrially.
  • the addition amount of the fluorosurfactant represented by the general formulas (5) to (7) may be appropriately determined according to the degree of requirement for preventing aggregation of the hydrophobic silica powder. It is 0.01-2 wt% with respect to hydrophilic silica, Preferably it is 0.05-: 1.5 wt%. 0. If less than Olwt%, the aggregation preventing effect may not be sufficiently obtained. On the other hand, the effect of the present invention can be obtained even when the addition amount of the fluorosurfactant exceeds 2 wt%, but the improvement degree of the effect obtained for the addition amount may be small, which is not preferable.
  • a polyalkylene glycol-based nonionic surfactant and naphthalene sulfonate-based surfactant that have been used conventionally are used.
  • a high molecular weight anionic surfactant such as lignin sulfonate or maleic acid copolymer may be used in combination with silicone oil.
  • silicone oils generally include non-reactive silicone oils having a linear siloxane structure, methylphenyl silicone oils, alkyl-modified silicone oils, polyether-modified silicones, and fatty acid ester-modified silicone oils.
  • Its kinematic viscosity is usually 1 to 100,000 mm 2 / s.
  • the loading amount of the surfactant and the silicone oil is usually 0.5 to 5 wt% with respect to the hydrophilic silica treated with the aminoalkylsilane compound.
  • A-1 N- (2-Aminoethyl) _3-aminominovir trimethoxysilane [Toray Silicone SH6020 (trade name), manufactured by Toray Dow Co. Silicone Co., Ltd.]
  • A-2 3-Aminopropyltriethoxysilane [Toray Silicone SS1040 (trade name), manufactured by Toray Dow Co., Ltd. Silicone Co., Ltd.]
  • AKD emulsion (AKD20wt% concentration) [made by Hakuto Co., Ltd.]
  • N Silicone oil emulsion (dimethylpolysiloxane 10wt% concentration) (Hakuto Co., Ltd.)
  • M Sodium perfluorooctyl sulfonate C F SO Na
  • a hydration reaction was performed. After 30 minutes, filtration was performed to obtain an aminoalkylsilane-treated product of hydrophilic silica. Next, add 300 g of beaker, 0.8 g of lauric acid (C), 0.5 g of dimethyl silicone oil (K), and lOOmL of toluene, stir, mix, and add hydrophilic silica treated with aminoalkylsilane. The mixture was stirred and stirred for 2 hours, and then heated to 90 to 110 ° C. to remove toluene-water azeotropically to obtain hydrophobic silica 1.
  • C lauric acid
  • K dimethyl silicone oil
  • hydrophilic silica treated with aminoalkylsilane The mixture was stirred and stirred for 2 hours, and then heated to 90 to 110 ° C. to remove toluene-water azeotropically to obtain hydrophobic silica 1.
  • hydrophilic silica treated with aminoalkylsilane prepared in the same manner as in Example 1 was added and azeotroped at 90 to 110 ° C. for 2 hours to obtain hydrophobic silica 2.
  • Example 2 2.5 g of stearic acid (D) was replaced with 2.5 g of alkyl ketene dimer (F) and added, and hydrophobic silica 3 was obtained in the same manner as in Example 2.
  • Example 5 In Example 4, 25 g of stearic acid emulsion (E) was replaced with 30 g of AKD emulsion (G), and hydrophobic silica 5 was obtained in the same manner as in Example 4.
  • Example 4 2 g of N— (2-aminoethyl) 1-3-aminopropyltrimethoxysilane (A) (0.4 g) (hydrophilic silica: 2 wt%), 5 g of stearic acid emulsion (E) 5 g, Hydrophobic silica 6 was obtained in the same manner as in Example 4 by adding 10 g of silicone oil emulsion (N) in place of 20 g.
  • Example 4 2 g of N— (2-aminoethyl) 1-3-aminopropyltrimethoxysilane (A) (4 g) (hydrophilic silica: 20 wt%), 50 g of 25 g of stearic acid emulsion (E), silicone 10 g of oil emulsion (N) was added in place of 5 g, and hydrophobic silica 7 was obtained in the same manner as in Example 4.
  • hydrophobic silica 8 Heated at 110 ° C. for 2 hours, and water and toluene were distilled off azeotropically to obtain hydrophobic silica 8.
  • the obtained hydrophobic silica 8 was put in a glass container and allowed to stand indoors at room temperature for 1 month. One month later, the glass container containing the hydrophobic silica 8 was shaken, and the aggregation state of the hydrophobic silica 8 was examined.
  • Hydrophobic silica 9 was hydrophobized in the same manner as in Example 8 without adding sodium perfluorooctyl sulfonate (M) 0.2 in Example 8, to obtain hydrophobic silica 9 .
  • the obtained hydrophobic silica 9 was placed in a glass container and allowed to stand indoors at room temperature for 1 month. 1 month Later, the glass container containing the hydrophobic silica 9 was shaken, and the aggregation state of the hydrophobic silica 9 was examined. As a result, several easily disintegrating lumps were observed.
  • Example 8 2.25 g of diisocyanate 4,4-diphenylmethane (1) was added instead of tolylene diisocyanate (H) to obtain hydrophobic silica 10.
  • hydrophobic silica 12 was obtained in the same manner as in Example 1.
  • a 500 mL three-necked flask equipped with a stirrer, thermometer and condenser is charged with 20 g of hydrophilic silica (B) and 2 g of dimethylpolysiloxane (K) and heated to 150 ° C for 1 hour under a nitrogen atmosphere. Thereafter, the mixture was cooled to obtain hydrophobic silica 13.
  • Comparative Example 1 instead of dimethylpolysiloxane (K) 1 .2 g, methylhydroxypolysiloxane (L) 1 .2 g was used and heated to 150 ° C. for 1 hour in a nitrogen atmosphere, and then cooled. Hydrophobic silica 14 was obtained.
  • reaction was performed for 2 hours. Subsequently, the mixture was heated at 90 to 110 ° C. for 2 hours to distill off water and toluene by azeotropic distillation, and then cooled to obtain hydrophobic silica 17.
  • hydrophobicity of hydrophobic silica was measured using the transmittance method described in JP-A-5-97423. Hydrophobic silica (lg) and water (lOOg) were placed in a 200mL separatory funnel, stirred for 5 minutes, and allowed to stand for 1 minute. 10 mL of suspended water was taken from the lower aqueous phase of the separatory funnel, and the transmittance at a wavelength of 550 nm was measured with an absorptiometer. The degree of hydrophobicity was determined by the following formula based on pure transmittance (100), and this value was used as the hydrophobicity of hydrophobic silica. The higher the degree of hydrophobicity, the higher the hydrophobicity.
  • hydrophobic silica of the present invention exhibits superior hydrophobicity as compared with conventional hydrophobic silica. It can also be seen that using a fluorosurfactant at the time of hydrophobization is effective in preventing aggregation of hydrophobic silica.

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  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
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Abstract

L'invention concerne une silice hautement hydrophobe pouvant être utilisée pour améliorer les performances anti-photovieillissement et de résistance à l'eau/résistance aux huiles de matériaux généraux de revêtement, pour améliorer les performances de prévention de l'adhérence de salissures (coquillages) de peintures de coques de navires, pour améliorer les propriétés de surface glissante et la résistance à l'usure de caoutchoucs et de résines et pour améliorer leur résistance mécanique, pour améliorer l'écoulement de toner dans des photocopieuses électrostatiques, pour améliorer les propriétés antimousses d'agents antimousses et pour améliorer les propriétés anti-adhérence dans la fabrication du papier. La silice hydrophobe est caractérisée en ce qu'elle est obtenue en traitant de la silice hydrophile avec un composé d'aminoalkylsilane, puis en faisant réagir la silice avec un ou plusieurs éléments choisis parmi des composés spécifiques d'acide carboxylique, des dimères d'alkylcétène et des composés de diisocyanate.
PCT/JP2006/306224 2006-03-28 2006-03-28 Silice hydrophobe WO2007110920A1 (fr)

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JP2008507308A JPWO2007110920A1 (ja) 2006-03-28 2006-03-28 疎水性シリカ

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Cited By (7)

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WO2009139502A1 (fr) * 2008-05-16 2009-11-19 キヤノン株式会社 Fine particule inorganique et hydrophobe et toner
JP2016020942A (ja) * 2014-07-14 2016-02-04 株式会社トクヤマ 正帯電性シリカ粒子及びその製造方法
JP2018104866A (ja) * 2016-12-28 2018-07-05 日華化学株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法
WO2020175159A1 (fr) * 2019-02-25 2020-09-03 日産化学株式会社 Particule d'oxyde inorganique, dispersion de particules d'oxyde inorganique et son procédé de préparation, et procédé de production d'un modificateur de surface
JP2020172564A (ja) * 2019-04-08 2020-10-22 ナトコ株式会社 フィラー粒子、膜形成用組成物、膜を備えた物品、成形用樹脂材料および成形品
WO2020255731A1 (fr) * 2019-06-19 2020-12-24 石原産業株式会社 Particules inorganiques revêtues en surface et leur procédé de production, et dispersion de solvant organique les contenant
WO2021075174A1 (fr) * 2019-10-16 2021-04-22 富士フイルム株式会社 Liquide de dispersion, composition, film durci, filtre coloré, élément optique, élément d'imagerie à semi-conducteur et unité de phare

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JP2016020942A (ja) * 2014-07-14 2016-02-04 株式会社トクヤマ 正帯電性シリカ粒子及びその製造方法
JP2018104866A (ja) * 2016-12-28 2018-07-05 日華化学株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法
KR20180077033A (ko) * 2016-12-28 2018-07-06 닛카카가쿠가부시키가이샤 발수제 조성물, 발수성 섬유 제품 및 발수성 섬유 제품의 제조 방법
KR102576864B1 (ko) * 2016-12-28 2023-09-12 닛카카가쿠가부시키가이샤 발수제 조성물, 발수성 섬유 제품 및 발수성 섬유 제품의 제조 방법
JP6995477B2 (ja) 2016-12-28 2022-01-14 日華化学株式会社 撥水剤組成物、撥水性繊維製品及び撥水性繊維製品の製造方法
JPWO2020175159A1 (fr) * 2019-02-25 2020-09-03
JP7464913B2 (ja) 2019-02-25 2024-04-10 日産化学株式会社 無機酸化物粒子、無機酸化物粒子分散液及びその製造方法、並びに表面修飾剤の製造方法
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WO2020175159A1 (fr) * 2019-02-25 2020-09-03 日産化学株式会社 Particule d'oxyde inorganique, dispersion de particules d'oxyde inorganique et son procédé de préparation, et procédé de production d'un modificateur de surface
JP2020172564A (ja) * 2019-04-08 2020-10-22 ナトコ株式会社 フィラー粒子、膜形成用組成物、膜を備えた物品、成形用樹脂材料および成形品
JP7266858B2 (ja) 2019-04-08 2023-05-01 ナトコ株式会社 フィラー粒子、膜形成用組成物、膜を備えた物品、成形用樹脂材料および成形品
WO2020255731A1 (fr) * 2019-06-19 2020-12-24 石原産業株式会社 Particules inorganiques revêtues en surface et leur procédé de production, et dispersion de solvant organique les contenant
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