KR101493979B1 - manufacturing method of hybrid materials using inorganic nano-particles - Google Patents

Abstract

The present invention provides a method for manufacturing organic and inorganic hybrid materials using inorganic nanoparticles, which disperses solid inorganic particles having micrometer size in a solvent, prepares uniform nanoparticles through uniformly pulverizing and drying the solid inorganic particles into inorganic particles having nanometer size using a miller or a pulverizer, disperses prepared inorganic nanoparticles in the solvent, surface-treats the inorganic nanoparticles with functional organic silane, and prepares solvent-dispersed functional inorganic nanosol.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing a hybrid inorganic-

More particularly, the present invention relates to a method for producing a hybrid inorganic or organic material using inorganic nanoparticles, and more particularly, to a method for producing inorganic nanoparticles by dispersing solid inorganic particles having a micrometer size in a solvent, And then uniformly pulverized and dried to form uniform nanoparticles. Then, the prepared nanosize inorganic particles are dispersed in a solvent and then surface-treated with functional organic silane on the inorganic nanoparticles to prepare a solvent-dispersed functional inorganic nano-sol And then the hybrid material is mixed with the functional organic resin to improve the mechanical abrasion resistance, denseness and durability of the material, as well as to induce the chemical bonding between the treated organic silane and the resin on the surface of the particles, The presence or absence of nano inorganic particles applicable to the required coatings and molded articles The present invention relates to a method for manufacturing a hybrid material.

In general, inorganic materials have excellent physical properties such as corrosion resistance, chemical resistance, abrasion resistance, heat resistance, hardness, moisture and gas barrier, and therefore they are actively utilized in the fields of structural materials, protective coating materials, abrasive materials and shielding films And the application range of inorganic materials having such excellent physical properties is required to be electric, electronic, information, and energy materials, and active research for application is under way.

In addition, not only the expensive high-temperature process and the dry process are required for the production of the inorganic material, but the inorganic material is difficult to produce the thick film due to the brittleness of the material itself and there are many limitations in applying the simple wet process.

In order to overcome these limitations, researches on the preparation of colloidal inorganic nano-sols capable of wet processing without deterioration of existing properties of inorganic materials and dispersion studies for application of inorganic materials to wet materials have been carried out. Was generally used as a structural material and it was able to improve the mechanical, thermal and chemical properties of inorganic materials by forming a hybrid organic material by mixing with a polymer resin such as an organic binder and then forming a film through wet coating.

However, in the case of the inorganic nano-sol prepared by the above-mentioned method, it is possible to produce the inorganic nano-sol from the starting material at a low temperature in a bottom-up manner, whereby the denseness of the inorganic material, the crystallinity of the structure, In order to overcome these problems, it is necessary to investigate the higher denseness and crystallinity of the inorganic particles and the high mechanical properties and chemical resistance thereof.

In order to satisfy the denseness and crystallinity of the inorganic nanoparticle sol, studies have been made to make liquid sols using hydrothermal synthesis and supercritical reaction which apply higher pressure and temperature than those in the liquid phase. There is a limit in the standardized reaction vessel in which the reaction temperature and the reaction pressure are increased to a level higher than a certain level required to raise the concentration of the inorganic nano- There are a lot of limitations in manufacturing an organic / inorganic hybrid material using high-precision high-crystal inorganic nanoparticles that can be produced through such a method.

BACKGROUND ART [0002] A conventional technique for manufacturing an organic / inorganic hybrid material is disclosed in Korean Patent Application Publication No. 10-2009-0120257 (published on November 24, 2009), entitled " Organic hybrid hybrid wet insulating film "has been introduced, and in Publication No. 10-2011-0134546 (published on December 15, 2011)," a method for producing a coating material in which a colloidal ceramic sol and an organic resin are hybridized and a coating film &Quot;, and a method for producing a hybrid material having refractive index controllability by controlling the particle size of silica nanosol is disclosed in Publication No. 10-2012-0118876 (published on October 30, 2012) , And "Hybrid packaging material manufacturing method" is disclosed in Korean Patent Registration No. 10-1269138 (Published on May 29, 2013).

In the above prior arts, inorganic nanosol, which is a starting material of an organic hybrid material, uses colloidal particles that have undergone sol reaction at room temperature from a ceramic precursor, and since the particle density is low, a problem may arise in mechanical properties , There is a problem that there is a complication in the process such as the step of substituting the organic solvent separately.

Therefore, nanometer-sized inorganic particles are produced through pulverization from inorganic particles having a micrometer-sized high crystallinity and denseness, and the prepared nanosilver particles are mixed with a solvent and then surface-treated with inorganic nanoparticles using a functional organosilane And an organic or inorganic hybrid material having high mechanical properties and chemical resistance which can be obtained by mixing with a functional organic resin after dispersing.

(Patent Document 1) Korean Patent Application Publication No. 10-2009-0120257 (published on November 24, 2009) (Document 2) Korean Patent Application Publication No. 10-2011-0134546 (Published Date December 15, 2011) (Document 3) Korean Patent Application Publication No. 10-2012-0118876 (Published date October 30, 2012) (Document 4) Korea Patent Office Registration No. 10-1269138 (Published on May 29, 2013)

DISCLOSURE Technical Problem Accordingly, the present invention has been made in order to solve the above-mentioned problems of the prior arts, and it is an object of the present invention to provide a method of manufacturing an inorganic particle by dispersing solid inorganic particles having a micrometer size in a solvent, The nanosized inorganic nanoparticles are dispersed in a solvent and then surface-treated with inorganic nanoparticles with a functional organosilane to produce functional inorganic nanosol dispersed in a solvent. And to provide a method for manufacturing an organic / inorganic hybrid material using the same.

According to an aspect of the present invention, there is provided a method for producing inorganic nanoparticles comprising: a first step of preparing inorganic nanoparticles; a step of dispersing the inorganic nanoparticles in a solvent and surface-treating the inorganic nanoparticles with the functional organic silane, And a third step of mixing the inorganic nano-sol of the second step with the functional organic resin to form an organic hybrid material. The hybrid inorganic nanoparticles may be prepared by a method comprising the steps of: The first step is to disperse solid inorganic particles having a crystallite size of micrometer in a solvent and then homogeneously pulverize them into nanometer sized inorganic particles by using a milling machine or a pulverizer, And then dried to form inorganic nanoparticles of uniform size. And the material preparation of a technical base.

The pulverization is preferably carried out by using a primary ball, and after the primary pulverization, secondary pulverization is preferably performed using a secondary ball having a relatively smaller size than the primary ball.

The inorganic particles in the first step are preferably one of silica, alumina, zirconia, and titania.

The solvent of the first step is preferably at least one of water, alcohol, toluene, acetone, cellosolve, thiepiepine, and ketone.

It is preferable that at least one of ball milling, speckle milling, and nanomilling is used for the grinding in the first step.

The organosilane in the two-stage process may be at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethyl Vinyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-hexyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, -Chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydride Hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltri Trialkoxysilanes composed of methoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and mixtures thereof, Ethoxy silane, dimethyl diethoxy silane, diethyl dimethoxy silane, Di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di- Di-n-pentyldimethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldimethoxysilane, di- Octyldimethoxysilane, di-n-octyldimethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, di Phenyldiethoxysilane, and dialkoxysilanes composed of a mixture thereof; and a mixture thereof.

The solvent of the second step is preferably at least one of water, alcohol, toluene, acetone, cellosolve, thiethiephene, and ketone.

The surface treatment in the second step is preferably carried out by a normal-temperature atmospheric pressure stirring reaction or a reflux stirring reaction.

The organic resin of the third step is an organic resin having a functional group capable of thermosetting and photo-curing, having at least one of epoxy group, amide group, imide group, urethane group, acrylic group, vinyl group and methacryl group desirable.

Accordingly, solid inorganic particles having a micrometer size are dispersed in a solvent, and uniform nanoparticles are prepared by uniformly pulverizing and drying the nanoparticles in the form of nanometer-sized inorganic particles using a mill or a mill, After dispersing the nanosized inorganic particles in a solvent, the functional inorganic silane nanocomposite is surface-treated with the functional organic silane to prepare a functional inorganic nanosol dispersed in a solvent. Then, a hybrid material is prepared by mixing with a functional organic resin to produce a mechanical abrasion resistance and dense And durability of the material can be enhanced, and also chemical bonding of the treated organic silane and resin to the surface of the particle is induced, which is applicable to coatings and molded articles requiring mechanical durability.

According to the present invention, the solid inorganic particles having a micrometer size are dispersed in a solvent, and then uniformly pulverized and dried in the form of nanometer-sized inorganic particles using a mill or a pulverizer to obtain uniform nanoparticles Dispersed in a solvent and then surface-treated with functional silane on the inorganic nanoparticles to prepare a solvent-dispersed functional inorganic nano-sol, followed by mixing with a functional organic resin to prepare a hybrid material , Mechanical abrasion resistance, denseness and durability of the material, as well as to induce chemical bonding between the treated organic silane and the resin on the surface of the particles, thereby being applicable to coatings and molded articles requiring mechanical durability.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an electron microscope photograph of inorganic silica particles having a size of several to several tens of micrometers according to an embodiment of the present invention.
FIG. 2 is an electron microscope photograph of inorganic silica nanoparticles having a size of several tens of nanometers manufactured by pulverization according to an embodiment of the present invention.
3 shows X-ray diffraction results of inorganic silica nanoparticles prepared by pulverization according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is an electron micrograph of an inorganic silica particle having a size of several to several tens of micrometers according to an embodiment of the present invention. FIG. 2 is a cross-sectional view of an inorganic silica particle having a size of several tens nanometers manufactured by pulverization according to an embodiment of the present invention FIG. 3 is an X-ray diffraction diagram of inorganic silica nanoparticles prepared by pulverization according to an embodiment of the present invention. FIG. 3 is a graph showing electron microscopic photographs of inorganic silica nanoparticles.

As shown in the drawings, the method for manufacturing an organic / inorganic hybrid material using nanosinner particles according to the present invention is characterized in that nanosized inorganic particles are produced and dispersed by pulverizing micro-inorganic particles having high density and crystallinity and high mechanical properties and chemical resistance A method of manufacturing a hybrid material having a micrometer size is firstly dispersed in a solvent and uniformly pulverized and dried in the form of nanometer sized inorganic particles using a milling machine and a pulverizer, (1); A second step of dispersing the nano-inorganic particles in the first step in a solvent, and then treating the surface of the nano-inorganic particles with the functional organosilane on the inorganic nanoparticles and then preparing a functional inorganic nano-sol having a solvent dispersed therein; And a third step of mixing the inorganic nano-sol of the second step with the functional organic resin.

First, the first step will be described.

An embodiment of the present invention provides inorganic silica particles having a particle size of several to several tens of micrometers as shown in FIG. The inorganic silica particles are inorganic particles obtained by direct re-sampling in a mine or by dividing inorganic silica particles collected through purification into re-collected particles by the particle size.

The inorganic silica particles were put into a nano milling machine together with water at a weight ratio of silica particles: water = 1: 4 and the zirconia balls were finally mixed at a weight ratio of particles: zirconia balls = 1: 5 and then milled at a total of 3000 rpm Go ahead.

In the first step, primary milled inorganic silica particles were milled for 3 hours using a zirconia ball having a size of 1 mm, and the primary milled inorganic silica particles were re-mixed in water and a zirconia ball, .

The size of the zirconia balls used in the second order is 0.1 mm. It was confirmed that the inorganic silica particles finally obtained through the milling had a uniform particle size of about 50 nmm as shown in Fig.

In order to confirm the crystallinity and compactness of the obtained inorganic silica particles having a nanometer size, it was confirmed by using an X-ray diffraction spectrometer. As a result, as shown in Fig. 3, quartz having excellent mechanical properties and chemical resistance And the half - width of the diffraction spectrum is narrow. Therefore, it can be confirmed that the structure is very dense.

Also, FIG. 3 shows that the change of the structure and the crystallinity of the material do not occur at all during the pulverization process of the particles and the high crystallinity and compactness are maintained.

Next, the second step according to the present invention proceeds.

The inorganic silica particles having the nanometer size obtained in the first step are dispersed in tetrahydrofuran (THF), and the primary and secondary silane treatment reactions are carried out at room temperature And 50 [deg.] C for 24 hours by the reflux method.

Upon completion of the reaction, the surface treatment of the inorganic nanoparticles is completed and the silane-treated inorganic silica nanosol dispersed in the solvent is produced. Here, the ratio of the inorganic silica nanoparticles to the silane and the solvent was 1: 0.3: 2.5, and 0.2 part of the silane ratio of 0.3 was methyltrimethoxysilane and the remaining 0.1 was the ratio of the aminotrimethoxysilane.

Next, the third step of the present invention proceeds.

In the examples of the present invention, the inorganic silica nanosol surface-treated with the primary and secondary organosilanes at 50 ° C was applied to an epoxy resin system (main component: bisphenol A, a carboxylic anhydride curing agent, polyglycol as a flow agent, tertiary amine as a curing catalyst at a pbw ratio of 100: 95: 15: 0.2) at a concentration of 10 wt% in an amount of 40 wt% Thereby forming an epoxy-silica organic hybrid material.

Next, the epoxy-silica organic hybrid material prepared in the above example was spin-coated on a glass substrate at 1000 rpm for 30 seconds, cured at 150 ° C for 120 minutes, and then cured at a thickness of about 10 袖 m. Samples were obtained.

Visible light transmittance, pencil hardness, and adhesion of the film were measured at room temperature using the obtained samples.

Table 1 below shows the results of physical properties according to the mixing amount of the inorganic silica nanosol.

Inorganic silica nanosol content 0wt% 10wt% 20wt% 30wt% 40wt% Permeability (%) 91 91 90 89 88 Pencil hardness 4H 5H 6H 7H 7H Adhesion 5B 5B 5B 4B 4B

The transmittance in Table 1 represents the average value measured in a wavelength range of 400 to 800 nm by UV-Vis spectroscopy. Pencil hardness and adhesive strength were measured according to ASTM standard and adhesive strength was measured by tape test.

As shown in Table 1, even though the content of inorganic nano-sol was increased by chemical crosslinking through hardening rather than simple mixing with epoxy through surface treatment of silica, there was no decrease in adhesive strength, and pencil hardness increased with increasing amount of silica nano-sol , Respectively. In addition, the optical transmittance was higher than 88% regardless of the mixing of the inorganic silica particles, and it was indirectly confirmed that the inorganic silica nanosol was well dispersed and dispersed in the epoxy system and evenly dispersed after curing without aggregation .

Silica nanoparticles prepared by pulverizing inorganic silica particles having high crystallinity and denseness through the physical property evaluation can be subjected to a silane hydrophobization treatment on the silica surface and a functional group capable of chemical crosslinking with the epoxy resin after the solvent dispersion to prepare an epoxy resin system It is possible to improve not only the efficiency in mixing, dispersing, coating, forming, and drying the resin composition, but also improving mechanical properties and optical properties.

Claims (9)

A second step of dispersing the inorganic nanoparticles in a solvent and surface-treating the inorganic nanoparticles with a functional organosilane to form a solvent-dispersed functional inorganic nano-sol; And a third step of mixing an inorganic nanosol with a functional organic resin to form an organic hybrid material, the method comprising the steps of:
In the first step, solid inorganic particles having a crystallite size of micrometer are dispersed in a solvent and then uniformly pulverized into nanometer-sized inorganic particles using a mill or a grinder, Forming inorganic nanoparticles of one size,
Wherein the pulverization is firstly pulverized using a primary ball, and after the primary pulverization, the secondary pulverization is carried out using a secondary ball having a size smaller than that of the primary ball. A method of manufacturing a hybrid material. delete The method according to claim 1, wherein the inorganic particles in the first step are one or more selected from the group consisting of silica, alumina, zirconia, and titania. The method according to claim 1, wherein the solvent in the first step is one or more selected from the group consisting of water, alcohol, toluene, acetone, cellosolve, thiethiepine, and ketone. Method of manufacturing a hybrid material. The method according to claim 1, wherein one or more selected from the group consisting of ball milling, speckle milling, and nano milling are used for the milling in the first step. The method according to claim 1, wherein the two-stage organosilane is selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n- Propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane , n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyl Triethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, Hydroxypropyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltrimethoxysilane, Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane , 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- ) Trialkoxysilane consisting of acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and mixtures thereof And dimethyldimethoxysilane, dimethyldiethoxysilane, di Di-n-propyldimethoxysilane, di-n-propyldimethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-propyldimethoxysilane, di- Butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di- Di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, A dialkoxy silane, a dialkoxy silane, a dialkoxy silane, a dimethoxy silane, a diphenyl diethoxy silane, and a dialkoxysilane composed of a mixture thereof, and a mixture thereof. The method according to claim 1, wherein the solvent of the second step is one or more selected from the group consisting of water, alcohol, toluene, acetone, cellosolve, Method for manufacturing hybrid organic / inorganic hybrid materials. The method according to claim 1, wherein the surface treatment of the second step is performed by a normal temperature atmospheric pressure stirring reaction or a reflux stirring reaction. The organic resin sheet according to claim 1, wherein the organic resin is a resin having a thermosetting and photo-curable functional group, and is selected from the group consisting of epoxy group, amide group, imide group, urethane group, acrylic group, vinyl group, Wherein the inorganic nanoparticle is an organic resin having a molecular weight greater than that of the nanoparticles.

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