KR100618129B1 - Producing method of surface modified oxide organosol - Google Patents

Abstract

The present invention relates to a method for preparing a surface-modified oxide organosol in which an oxide particle surface in an oxide sol in which nano-sized metal oxide fine particles are dispersed in a solvent is modified with reactive and non-reactive functional groups. Oxide organosol dispersed in an oxide aqueous sol or organic solvent is used as a starting material, and the organosilane reacts with a hydroxyl group on the surface of the oxide particle, and then silylated and unreacted organosilane and silane are condensed by ultrafiltration. The present invention relates to a method of preparing a surface-modified oxide organosol by removing a silane condensate having a high molecular weight or water.

Surface Modification, Oxide Organosol, Ultrafiltration

Description

Producing method of surface modified oxide organosol

1 is a graph illustrating the viscosity change over time of the coating material prepared by Preparation Example 1, Preparation Example 2, Preparation Example 3 of the present invention.

Figure 2 is a graph illustrating the viscosity change over time of the coating material prepared by Preparation Example 4, Preparation Example 5, Preparation Example 6 of the present invention.

The present invention relates to a method for preparing a surface-modified oxide sol in which the surface of a metal oxide fine particle is modified with a reactive or non-reactive functional group. More particularly, the present invention relates to an oxide organo dispersed in an oxide aqueous sol or an organic solvent using water as a dispersion medium. The present invention relates to a method for producing a surface-modified oxide organosol excellent in compatibility with, dispersibility, and storage stability with various organic solvents and organic substances having different polarities.

Various oxide sol is organic / inorganic composite material in the field of surface treatment agent such as ceramic, glass, plastic, wood or plastic reinforcing agent, binder, adhesive, paint, resin processing, electric and electronic material according to the characteristics of metal oxide contained It may be used in various combinations for the purpose of the additives. Oxide sol that can be used industrially useful at present, such as silica sol, titania sol, antimoniazole, zirconia sol, alumina sol and ceria sol, etc. In addition, the application range is gradually expanded for various metal oxides. . However, since the particle surface of the oxide sol is mainly a hydroxyl group, the mixing and dispersion of the non-polar organic solvent and various organic substances are limited, and since the mixing and reaction with the organic substances are impossible, they are limited to being used for organic inorganic composite materials. There is.

In order to improve the dispersibility, miscibility, and reactivity with these organic substances and to apply them to the organic industry, the surface of the oxide sol should be modified and used.

Among various oxide sols, it is known that surface modification techniques for silica sol can be prepared by various methods. Conventionally, as a method for producing a surface-modified silica organosol, Japanese Unexamined Patent Publication No. 50-96699 adds an organosylating agent to a solution obtained by distilling and separating siloxysilanol from a neutralized aqueous solution of water glass with a polar organic solvent. Although a method of neutralizing water glass has been proposed, incorporation of sodium salts is unavoidable because of the process of neutralizing water glass, it is difficult to obtain a highly stable silica organosol due to the relatively high amount of water remaining and the low molecular weight of silica. In addition, since there is a process of distilling and separating the siloxysilanol, the utilization rate of silica contained in the water glass as a raw material is reduced, and the yield of silica sol production is lowered. Therefore, it is not only possible to obtain silica organosol at a low cost, but also the reproducibility of the work. There is also a disadvantage.

Japanese Patent Application Laid-Open No. 58-145614 discloses a silica organosol having a particle diameter of 5 to 30 nm by solvent replacement to prepare a silica organosol having a water content of 10% or less, reacting with an organosilylating agent, and then removing the solvent to remove silica. Although it has been described to obtain a silica powder that is redispersible in an organic solvent in which a silyl group is chemically bonded to the particle surface, silica having a uniform particle size distribution is generated due to coagulation and bonding between particles during the process of drying and powdering the sol. There is a problem with getting a sol.

US Pat. No. 4,417,15 discloses a method of hydrolyzing an alkyltrialkoxysilane with water or an acidic aqueous solution and then mixing with an aqueous silica sol to react the alkyltrialkoxysilane with silica to use it as a component of the coating paint. By the condensation reaction between silanes before the reaction with silane, a large molecular weight silane condensate is produced, and it is difficult for silica and silane to react with high efficiency, and large particles of silica are produced, resulting in a decrease in dispersibility in a nonpolar organic solvent. .

U.S. Pat.No.5651921 describes the addition of a pH titrant to lower alcohols in a silica aqueous sol titrated to pH 1-5, followed by removal of water by azeotropic distillation to produce an alcohol dispersed silica sol, which is non-polar to the alcohol dispersed silica sol. After adding an organic solvent, a silica organosol dispersed in a nonpolar organic solvent is prepared by solvent replacement, and the surface of the silica-modified sol of the sol thus prepared is subjected to cylylation with organosilane. After preparing the silica aqueous sol to pH 1-5 with pH titrant, an emulsion is formed by adding a nonpolar organic solvent and a cationic surfactant, and then water is removed by azeotropic distillation to disperse the colloidal silica sol dispersed in the nonpolar organic solvent. And preparing a surface-modified silica organosol by silylating the surface of silica particles with organosilane. Although unreacted alkoxysilanes and silane condensates which remain unbound with silica have been disclosed, it is difficult to remove these unreacted alkoxysilanes and silane condensates when used in coating materials. There is a problem that harms and adversely affects the physical, thermal and chemical properties of the final cured coating. In addition, in the non-polar organic solvent, the surface of the silica particles may be subjected to the cyrillation treatment, which is likely to cause particle aggregation of the silica sol, and thus it is difficult to obtain a low viscosity, high concentration silica sol that is stably dispersed even after the surface modification treatment. There is a problem that the use range is limited.

In order to prevent particle agglomeration generated in the case of cylylation treatment in a non-polar organic solvent, Japanese Laid-Open Patent Publication No. 11-43319 discloses a hydrophilic colloidal silica and a silylating agent such as a disiloxane compound or a monoalkoxysilane compound and a hydrophobic organic solvent. The surface of the silica particles is silylated by subjecting the reaction mixture containing C1 to C3 alcohol and water to mature in the range of 0 to 100 DEG C while removing the alkali present in the reaction mixture or neutralizing it with an equivalent acid or more. After forming the treated silica organosol, the method of preparing the surface-modified silica organosol dispersed in the hydrophobic organic solvent by performing solvent replacement with a hydrophobic organic solvent is described, but the condensation of unreacted organosilane and silane It is difficult to solve various problems caused by the remaining.

In order to solve this conventional problem, an object of the present invention is a surface-modified oxide organosol in which the surface of an oxide particle is silylated with organosilane from a conventional oxide aqueous sol or organosol which is commercially available or prepared by a known method. It can be prepared to improve the dispersibility, storage stability, purity, recovery rate, etc., and can provide a method for producing surface-modified oxide organosol in terms of manufacturing equipment and energy.

In addition, another object of the present invention is to provide a method for preparing a surface-modified oxide organosol having improved dispersibility and storage stability by removing unreacted material after the cyrilization reaction.

Another object of the present invention is to mix the surface-modified oxide organosol prepared above with various organic solvents and organic resins having different polarities, such as mechanical, physical, thermal properties and compatibility with resins or solvents that are difficult to implement only organic materials and It is to provide a resin having improved dispersion stability and storage stability.

In order to achieve the above object, the present inventors perform silylation reaction using colloidal oxide aqueous sol or organosol prepared by a conventional method as a starting material, and remove impurities such as uncoagulant and a solvent by ultrafiltration, and storage stability and A surface modified oxide organo sol having improved dispersion stability was prepared.

The present invention comprises i) treating an aqueous oxide sol or organosol having an average particle diameter of 5 to 300 nm and an oxide solid concentration of 5 to 50% by weight with a cation exchange resin and an anion exchange resin, or by adding a pH titrant to pH 7 Acidification to less than;

Ii) adding a organosilane represented by the following formula (1) or a hydroxysilane obtained by hydrolysis thereof to the acidified oxide sol to surface-modify the surface of the oxide particles by subjecting it to a silylation reaction;

R ¹ _c SiR ² _{4- c}

[Wherein c is an integer of 0 to 3,

R ¹ has an alkyl group, a ketone group, an acryl group, an allyl group, an aromatic group, a halogen group, an amine group, an amino group, a mercapto group, an ether group, a straight chain, branched chain, or cyclic group having two or more kinds of an ester group or an epoxy group. It is a compound of 1 to 10 carbon atoms,

R <^2> is a C1-C6 compound which has a hydrogen, an alkoxy group, a ketone group, a halogen group, or an amine group individually or in 2 or more types.]

Iv) adding an organic solvent to the surface-modified oxide sol and then performing ultrafiltration to remove excess organic solvent, water, unreacted organosilane, condensate between silanes or alkali ions; It relates to a method for producing a surface-modified oxide organosol comprising a.

The average particle diameter of the oxide aqueous sol or organosol suitable for the present invention is 5 to 300 nm, preferably 10 to 200 nm, and the solid content concentration of the oxide in the colloidal sol is 5 to 50% by weight, preferably Use 5-40% by weight. Using an oxide sol outside the average particle diameter of the above range reduces the stability of the oxide particles of the final product organosol, If the concentration exceeds 50% by weight, the viscosity of the sol rises, the recovery rate decreases, and storage stability is also poor.

In addition, when the aqueous sol is used in the i) process, the acid sol stabilized with acid is used as it is, and the alkaline oxide sol stabilized with alkali is used after acidification. In order to acidify an alkaline oxide sol, it is titrated to less than pH 7 using an ion exchange resin or a titrating agent. Even in the case of using an organosol, the pH is used in an acidic range.

When the oxide sol has a pH of 7 or more, the hydrolysis reaction of the oxide sol is slow, and the condensation reaction between the silanes is superior to the amount of the hydrolyzate bonded to the silica, so that a condensate having a high molecular weight is formed, which is insufficient for surface modification of the silica particles. Do.

The cation exchange resin used here is a hydrogen type strong acid cation exchange resin, and an anion exchange resin uses a hydroxyl type strong base anion exchange resin. The ion exchange resin after ion exchange is hydrochloric acid and sulfuric acid, and anion exchange resin. Caustic soda can be recycled and used respectively.

The pH titrant is unsaturated, saturated or carboxylic anhydride. Examples of these carboxylic acids include acetic acid, itaconic acid, maleic acid, formic acid, propionic acid, benzoic anhydride, succinic acid, 1,3,5-benzenetricarbon. Acids, 1,2,4,5-benzenetetracarboxylic acid, and the like, and examples of the anhydrous carbonic acid include itaconic anhydride and maleic anhydride. Trimellitic anhydride, pyromellitic anhydride, a phthalic anhydride etc. are mentioned.

In addition, the present invention is the oxide is represented by the formula (2),

M _a O _b

[a, b are integers greater than or equal to 0; M is metal]

Silicon oxide, titanium oxide, antimony oxide, zirconium oxide, aluminum oxide, cerium oxide, indium oxide, tin oxide, iron oxide group is characterized in that one or two or more complex oxides.

In addition, the present invention, the organosilane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltri Methoxysilane, vinyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, diphenylethoxyvinylsilane, tetramethoxysilane, tetrae Methoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- ( 3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acryloxypropyl Dimethylmethoxysilane, 3-acryloxypropyl Methylethoxysilane, 3-acryloxypropyldimethylpropoxysilane, 3-acryloxypropylmethylbis (trimethylsiloxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -Acryloxypropyltripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane or 3- (meth) acryloxypropyltripropoxysilane, N- (2-aminoethyl-3-aminopropyl) -trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) -triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, trimethoxysilylpropyldiethylenetriamine, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Ethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltris ( Methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropylphenyldiethoxysilane, heptadecafluorodecyltrimethoxysilane, methyltrichlorosilane, dimethyl Dichlorosilane, trimethylchlorosilane, ethyltrichlorosilane, diethyldichlorosilane, triethylchlorosilane, vinyltrichlorosilane, stearyltrichlorosilane, dihexyldichlorosilane, diphenyldichlorosilane, triphenylchlorosilane, n It is characterized by using 1 type (s) or 2 or more types chosen from the group which consists of amyl trichlorosilane and hexamethyldisilazane.

In addition, the present invention is characterized in that the cylylation reaction adds 0.01 to 4 moles of organosilane per 100,000 m 2 of the surface area of the oxide particles contained in the oxide sol and reacts at 0 to 100 ° C.

In addition, the present invention is an organic solvent of the step iii) the alcohol containing methanol, ethanol, propanol, ethers containing dimethyl ether, acetone, ketones containing methyl ethyl ketone, esters containing ethyl acetate or It is characterized by the cellosolves containing 2-ethoxy ethanol.

In addition, the present invention is characterized in that the fractional molecular weight of the ultrafiltration membrane is less than 300,000 in the step iii).

In addition, the present invention, the material of the ultrafiltration membrane of step iii) is polysulfone, polyacrylonitrile, polyamide, polyethersulfone, acetyl cellulose, nitrocellulose, organic material containing cellulose, SiO ₂ / Al ₂ O _{And at} least one member selected from the group consisting of a ceramic material containing ₃ and a graphite material containing graphite / Al ₂ O ₃ .

Furthermore, the present invention is characterized in that the pressure in the step iii) the ultrafiltration operation is in the range of 2 ~ 10kgf / ㎠.

The shape of the ultrafiltration membrane is not particularly limited, but preferably, a flat membrane, a tubular membrane, a hollow fiber membrane, a spiral membrane, or the like may be used. When operating the ultrafiltration device, the pressure is applied to the filtration membrane. The pressure is in the range of 2 to 10 kgf / cm 2, and if the operation is performed at an excessive pressure during operation, deposition of oxide particles may occur on the surface of the filtration membrane. However, it is desirable not to operate above the pressure at which permeate flow is economically feasible and feasible.

The ultrafiltration process of the present invention is a step of concentrating again after mixing an organic solvent with a reaction product of an oxide sol and an organosilane, and during this process, water, organic solvent, and unreacted silane are removed through fine pores of the ultrafiltration membrane. do. At this time, since the organic solvent is easily volatilized, it can be carried out at low temperature or in a sealed state. The reactant and the organic solvent may be mixed first, followed by an ultrafiltration step, or may be equipped with a dropping system to continuously add the organic solvent and then perform the ultrafiltration step.

In order to prepare the surface modified oxide organosol according to the present invention, the surface area of the oxide particles containing the organosilane in the metal oxide sol after acidifying the oxide aqueous sol or organosol containing the metal oxide colloid particles to less than pH 7 When the reaction is carried out by adding 0.01 to 4 molar weight, preferably 0.03 to 2 molar weight per 100,000 m ² , the surface-modified oxide sol in which the surface of the oxide particles is silylated with organosilane can be obtained. If the organosilane is less than 0.01 mole weight, there is a limitation in application because the surface of the oxide particle is not completely silylated. If the amount of the organosilane is more than 4 mole, the silylation of the surface of the oxide particle is complete, but the unreacted silane remaining after the reaction And because the condensate of the silane is filtered out during the ultrafiltration process, it is not economical, the condensate of the organosilane has a problem that the process time increases because the molecular weight and the viscosity increases.

The reaction temperature in which the surface of the metal oxide particles is silylated with organosilane is carried out in the range of 0 to 100 ° C, preferably causing a reaction in the range of 20 to 80 ° C. At temperatures below 0 ° C, the surface reaction of the particles of the oxide sol and organosilanes is insufficient to induce reactions.At temperatures above 100 ° C, collisions and bonds between the oxide particles occur and the particles are deformed or uniform and stable. It is not desirable to obtain. In addition, since the reaction temperature and the reaction time are inversely related, the surface modification reaction is carried out at an economically favorable temperature and time. In the oxide sol thus prepared, not only the oxide particles whose surface is silylated with organosilane, but also condensates of unreacted organosilane and silane are present.

The surface-modified oxide sol in which the surface of the oxide particles obtained by the silylation reaction is silylated with organosilane is unreacted organosilane and silane condensate by an ultrafiltration device composed of a stirrer, a pump, a filter membrane, a pressure gauge, and the like. , Moisture and the like are removed to form an organosol.

In addition, when the aqueous sol stabilized with alkali is used as a starting material, alkali ions contained as stabilizers are released through the pores of the membrane during the ultrafiltration process, thereby producing a highly purified surface modified oxide organosol. The ultrafiltration process repeats the process of adding an organic solvent and performing ultrafiltration several times. Since the dilution and concentration process are repeated, it is also possible to replace the aqueous sol with the organosol dispersed in the organic solvent. It is also possible to substitute the organosol dispersed in the organic solvent different from the original solvent, and the higher the number of times the dilution and concentration process is repeated, the more highly sol can be produced.

In addition, it is also possible to increase the concentration of the organosol by continuing the operation during the concentration process, but the excessive concentration to the concentration of the solid content to 50% by weight or less because it is a factor that inhibits the stability of the oxide sol. After recovering the surface-modified oxide organosol, the final product, backwashing is performed to increase the life of the filter membrane and the efficiency of the filtration and permeating oxide sol during the filtration operation. Backwashing acts to desorb the oxide particles that may be attached to the pores or wall of the membrane by introducing the solvent in the direction opposite to the direction through which the solvent is permeated.

The present invention will be specifically described by the following examples and comparative examples. However, the scope of the present invention is not limited to the description of the examples.

Example 1

Alkaline aqueous silica sol (SiO ₂ content 30wt.%, Na ₂ O content 0.4wt.%, PH 9.7, particle size 15nm, specific surface area 250m ² / gr) prepared by a known method or commercially available, while stirring 1,330gr well After adding 120 gr of acetic acid and titrating to pH 4.2, 354.5 gr (1.5 mole weight) of 3-glycidoxypropyltrimethoxysilane was added, and the mixture was reacted at 60 DEG C for 7 hours to cyrilize the silica particle surface. . 1800 ml of ethanol was added to the reaction mixture, and the mixture was stirred and mixed thoroughly. When the permeate reached 1,800 ml, the operation was stopped, and 1,800 ml of ethanol was added to the reaction mixture, mixed thoroughly, and filtered again six times to obtain silica organosol having the surface of the surface modified with an epoxy group. .

The water content in the surface-modified silica organosol was 0.8% by weight using the Karl Fischer method, and the Na content was determined by atomic absorption method at 85 ppm. The Brookfield DV-E Viscometer (BROOKFIELD DV-E VISCOMETER) The viscosity measured at 20 ° C. was 3.2 cPs.

Example 2

A commercially available antimony oxide organosol (Sb ₂ O ₅ content 30wt.%, Methanol dispersion type, pH 8, particle size 10nm, specific surface area 300m ² / gr) 1,110gr was added, titrated to pH 3.5 by adding 33gr maleic anhydride well, 198.7 gr (0.8 mole weight) of 3-methacryloxypropyltrimethoxysilane was added, and the mixture was stirred at 20 ° C. for 4 hours, and aged for 12 hours to cyrilize the surface of the antimony oxide particles. 1300 ml of methanol was added to the reaction mixture, and the mixture was stirred and mixed thoroughly. When the permeate reached 1,300 ml, the operation was stopped, and 1,300 ml of methanol was added to the reactant, mixed thoroughly, and filtered again. The antimony oxide organosol having the surface of the particle modified with methacrylic surface was repeated once more. Obtained. The viscosity measured at 20 degreeC with the Brookfield DV-E VISCOMETER was 4.1 cPs.

Comparative Example 1

Silica organosol was prepared in the same manner as in Example 1, except that the amount of 3-glycidoxypropyltrimethoxysilane added in the cylylation treatment was 0.01 molar weight.

Moisture content in the silica organosol was 0.9% by weight using Karl Fischer's method, Na content was measured by atomic absorption method, and 87ppm. 20 was determined by Brookfield DV-E Viscometer (BROOKFIELD DV-E VISCOMETER). The viscosity measured at ° C was 2.6 cPs.

Comparative Example 2

2,000 ml of an alkaline aqueous silica sol (SiO ₂ content 30wt.%, Na ₂ O content 0.4wt.%, PH 9.7, particle size 10-20nm) prepared by a known method or commercially available is filled with a hydrogen type strong acid cation exchange resin. The solution was passed through an ion exchange resin column, and then into an ion exchange resin column filled with a hydroxyl type strong base anion exchange resin. After adding 20.8 gr of reagent-grade nitric acid to the silica sol obtained by ion exchange, adjusted to pH 1.2, and aged at room temperature for 36 hours, the cation exchange resin and the anion exchange resin were passed through once more. Finally, the cation exchange resin was further passed through once more. 1,500 ml of methanol was added to 1,500 ml of the aqueous silica sol subjected to the ion exchange as described above, and the mixture was stirred and mixed thoroughly, followed by filtration and dehydration at a pressure of 2 kgf / cm 2 using an ultrafiltration membrane (fraction molecular weight 100,000). When the permeate was 1,500 ml, the operation was stopped, 1,500 ml of methanol was added to the silica sol, mixed thoroughly, and filtered and dewatered again. This operation was repeated seven times to obtain silica organosol dispersed in methanol. The water content in the silica organosol was 0.9% by weight using the Karl Fischer method, and the Na content was measured by atomic absorption method at 75 ppm. The content was 20 with a Brookfield DV-E Viscometer. The viscosity measured at ° C was 2.4 cPs.

Comparative Example 3

A surface-modified antimony oxide organosol was prepared in the same manner as in Example 2 except that the unreacted organosilane and silane condensate were not removed by ultrafiltration. The viscosity measured at 20 ° C. with a Brookfield DV-E VISCOMETER was 5.8 cPs.

In order to verify the effect of the surface modified oxide organosol prepared by Examples 1 and 2, Comparative Examples 1 to 3 of the present invention was applied as an additive of the organic matter as follows.

[Production Example 1]

A photosensitive epoxy coating was prepared by mixing 500 g of a phenol novolac epoxy resin with an epoxy equivalent of 180 to 190, 200 g of 2-ethylhexyl vinyl ether as a reactive diluent, 20 gr of SbF6-based aromatic sulfone salt as a polymerization initiator, and 700 ml of toluene as a diluting solvent. Thereafter, 800 g of the surface-modified silica organosol prepared in Example 1 was added to prepare an organic-inorganic composite coating paint. The results of observing the dispersion stability and storage stability of the coating paints are shown in Table 1 and FIG. 1.

[Production Example 2]

A coating material was prepared in the same manner as in Preparation Example 1, except that silica organosol to be added was prepared according to Comparative Example 1. The results of observing the dispersion stability and the storage stability of the coating coating are shown in Table 1 and FIG.

[Manufacture example 3]

A coating paint was prepared in the same manner as in Preparation Example 1, except that the silica organosol to be added was prepared according to Comparative Example 2. The results of observing the dispersion stability and the storage stability of the coating coating are shown in Table 1 and FIG.

[Production Example 4]

Commercial urethane acrylate oligomer (Miwon Co., Ltd., MIRAMER PU-610) 500 gr and dipentaerythritol hexaacrylate 300 gr as an acrylate monomer, 1,6-hexanediol diacrylate 200 gr, 1-hydroxy as a photoinitiator Roxy-cyclohexyl-phenyl ketone 40gr, methyl ethyl ketone 1,000gr as a dilution solvent was mixed to prepare a UV-curable coating paint, and then the surface-modified antimony oxide organosol 1,500gr prepared in Example 2 was added to the organic inorganic compound Coating paints were prepared. The coating was applied to a PMMA acrylic plate with a thickness of 8 mm by bar coating using a # 08 Mayer bar, dried at 70 ° C. for 30 seconds using a hot air dryer, and then exposed to a high pressure mercury lamp in the air at 800 mJ / cm ² for thickness 7 A coating film of μm was obtained. Table 2 and FIG. 2 show the results of evaluating the properties of the coating and coating films.

Production Example 5

A coating paint and a coating film were obtained in the same manner as in Preparation Example 4, except that the antimony oxide organosol to be added was prepared according to Comparative Example 3. Table 2 and FIG. 2 show the results of evaluating the properties of the coating and coating films.

[Manufacture example 6]

A coating paint and a coating film were obtained in the same manner as in Preparation Example 4, except that the antimony oxide organosol to be added was used without a surface modified state. Table 2 and FIG. 2 show the results of evaluating the properties of the coating and coating films.

1. Dispersion stability: After adding oxide organosol to organic coating, the change of appearance was visually observed to evaluate whether it was transparent or cloudy.

O: Excellent compatibility with transparent dispersion without layer separation or discoloration

(Triangle | delta): Although it disperse | distributes transparently, what has a raise of a viscosity

X: The paint becomes cloudy and the compatibility is not good

2. Storage stability: Viscosity change over time of the final organic inorganic coating paint was measured at 20 ℃ with a Brookfield DV-E viscometer (BROOKFIELD DV-E VISCOMETER). The storage stability was determined after measuring the viscosity change of 7 days.

O: viscosity change falls within 10% of initial value

△: viscosity change falls within 20% of initial value

X: Viscosity change increased more than 10% of initial value

3. Evaluation of physical properties of coating film

3-1. Abrasion resistance: Taber wear of the coating film coated on the PMMA plate was performed according to ASTM D1044. Haze was measured by observing worn specimens with Haze gard plus (BYK gardner Co.) at room temperature for 500 turns with a CS-10F wheel at 50 gr weight.

3-2. Chemical resistance (alkali and acidic): The alkali resistance was observed by visually changing the coating film after immersing a PMMA plate coated in a 5% NaOH aqueous solution at room temperature for 12 hours. Acid resistance was observed after visually immersing the PMMA plate coated with 10% sulfuric acid aqueous solution at room temperature for 12 hours.

O: No change in appearance of coating film

(Triangle | delta): Fine points generate | occur | produce in a coating film

X: The phenomenon that the coating film peels off occurs.

3-3. Weatherability: The coating film was accelerated by using a weathering tester (QUV, Q-PANEL) at 50 ° C. for 100 hours at 15MJ UV energy irradiation, and then the appearance of the coating film was visually observed.

O: No change in appearance of coating film

(Triangle | delta): Fine points generate | occur | produce in a coating film

X: Cracking in Coating Coating Film

 division  Preparation Example 1  Preparation Example 2  Preparation Example 3  Oxide Sol Used in Manufacturing  Example 1  Comparative Example 1  Comparative Example 2  Dispersion stability  O  △  X   Viscosity (cps)  Right after manufacturing  10.1  13.9  21.6  7 days later  10.9  101.6  150.3  Storage stability  O  X  X

 division  Preparation Example 4  Preparation Example 5  Preparation Example 6  Oxide Sol Used in Manufacturing  Example 2  Comparative Example 3  No surface modification  Dispersion stability  O  O  △  Viscosity (cps) Right after manufacturing  4.2  4.3  5.1 7 days later  4.3  5.1  11.2 Storage stability  O  △  X  Abrasion Resistance (△% Haze)  4  7  16  Chemical resistance Alkali resistance  O  X  X Acid resistance  O  O  X  Weather resistance  O  △  X

As described above, the surface-modified oxide organosol prepared by the present invention has an unreacted substance or surface which has a surface modified with reactive or non-reactive functional groups, and which has limited application to various fields. By removing the remaining condensate, it is excellent in compatibility with various organic solvents and organic resins with different polarity, dispersion stability, storage stability, and mechanical, physical and thermal characteristics which are difficult to realize only with organic materials. There is an advantage, it can be applied to a wide range of industries.

Claims (8)

i) Oxide aqueous sol or organosol having an average particle diameter of 5 to 300 nm and an oxide solid concentration of 5 to 50 wt% is treated with a cation exchange resin and an anion exchange resin or acidified to less than pH 7 by addition of a pH titrant. Process of doing; Ii) adding an organosilane represented by the following general formula (1) or a hydroxysilane obtained by hydrolysis thereof to the acidified oxide sol to perform a surface modification by subjecting the surface of the oxide particles to a silylation reaction; R ¹ _c SiR ² _{4- c} (1) [Wherein c is an integer of 0 to 3, R ¹ has an alkyl group, a ketone group, an acryl group, an allyl group, an aromatic group, a halogen group, an amine group, an amino group, a mercapto group, an ether group, a straight chain, branched chain, or cyclic group having two or more kinds of an ester group or an epoxy group. A compound having 1 to 10 carbon atoms, R ² is hydrogen or alkoxy group, ketone group, halogen group or compound having 1 to 6 carbon atoms having two or more amine groups] Iv) adding an organic solvent to the surface-modified oxide sol and then performing ultrafiltration to remove excess organic solvent, water, unreacted organosilane, condensate between silanes or alkali ions; Method of producing a surface-modified oxide organosol comprising a. The method of claim 1, wherein the oxide is one or two or more complex oxides selected from silicon oxide, titanium oxide, antimony oxide, zirconium oxide, aluminum oxide, cerium oxide, indium oxide, tin oxide or iron oxide. Method of producing a surface-modified oxide organosol. The method of claim 1, wherein the organosilane is methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltri Ethoxysilane, vinyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, diphenylethoxyvinylsilane, tetramethoxysilane, Tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N -(3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acrylic Oxypropyldimethylmethoxysilane, 3-acryloxypropyldi Methylethoxysilane, 3-acryloxypropyldimethylpropoxysilane, 3-acryloxypropylmethylbis (trimethylsiloxy) silane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3 -Acryloxypropyltripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane or 3- (meth) acryloxypropyltripropoxysilane, N- (2-aminoethyl-3-aminopropyl) -trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) -triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, chloropropyltrimethoxysilane, chloropropyltriethoxysilane, trimethoxysilylpropyldiethylenetriamine, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Ethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltris ( Methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropylphenyldiethoxysilane, heptadecafluorodecyltrimethoxysilane, methyltrichlorosilane, dimethyl Dichlorosilane, trimethylchlorosilane, ethyltrichlorosilane, diethyldichlorosilane, triethylchlorosilane, vinyltrichlorosilane, stearyltrichlorosilane, dihexyldichlorosilane, diphenyldichlorosilane, triphenylchlorosilane, n- A method for producing a surface-modified oxide organosol, characterized in that one or two or more selected from the group consisting of amyl trichlorosilane and hexamethyldisilazane are used. delete delete delete delete delete

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