KR20180032822A - Organic-inorganic nanohybrid coating agent and resin containing silica nanoparticles treated by silicone-modified oligomer, and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an organic-inorganic nanohybrid coating agent comprising silica nanoparticles surface-modified by a silicone-modified oligomer, an organic-inorganic nanohybrid resin comprising silica nanoparticles surface-modified by the silicone-modified oligomer, and manufacturing methods thereof. The manufacturing method of the organic-inorganic nanohybrid coating agent comprising the silica nanoparticles surface-modified by the silicone-modified oligomer of the present invention comprises the steps of: preparing the silicone-modified oligomer including a nitrogen element; protecting one end of the silicone-modified oligomer by using a protective group; mixing surface-treated silica nanoparticles with the silicone-modified oligomer to obtain the silica nanoparticles surface-modified by the silicone-modified oligomer; and mixing the silica nanoparticles surface-modified by the silicone-modified oligomer with a polymer including nitrogen element, wherein the silicone-modified oligomer is obtained by using one or more of a first silicone reactant and a second silicone reactant comprised of silicone monomers or silicone oligomers as a first monomer and a second monomer when performing a condensation polymerization reaction between the first monomer of which ends include at least one of isocyanate and amine group and the second monomer of which ends include at least one of acid anhydride, carboxylic acid and carboxylic acid chloride under an organic solvent. Therefore, the organic-inorganic nanohybrid coating agent and the organic-inorganic nanohybrid resin comprising the silica nanoparticles surface-modified by the silicone-modified oligomer manufactured by the methods according to the present invention provide effects that adhesive properties and impact resistance of the coating agent and the resin are improved by chain entanglement between the oligomer and the polymer and an increase in flexibility of the oligomer due to silicone modification.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic nano hybrid coating agent, a resin, and a manufacturing method thereof, which comprises silica nanoparticles surface-modified with a silicone modified oligomer,

The present invention relates to an organic or inorganic nanohybrid coating, a resin and a method for producing the same, and more particularly, to an organic or inorganic nanohybrid coating comprising a silica nanoparticle surface-modified with a silicone modified oligomer, And nanohybrid coatings comprising the silica nanoparticles surface-modified with an oligomer which improves adhesion and mechanical strength.

In order to enhance the electrical, mechanical, and thermal properties of the polymer resin, researches on techniques for complexing inorganic nanoparticles have been carried out steadily, and research on the development of nanohybrid materials using silica nanoparticles has been widely performed. In developing such nanohybrid materials, silica surface treatment is very important for bonding between organic and inorganic materials and securing the dispersibility of silica nanoparticles. In the case of the silica surface treatment, a substance of 2 to 3 -valent silane known as a silane coupling agent is widely used as in the 'Korean Patent Registration No. 10-0945198 Organic Solvent Type Silica Sol and its Production Method' , An organic or inorganic nano hybrid coating material containing silica nanoparticles surface-modified with an oligomer, a resin and a process for preparing the same] for the purpose of improving bonding strength and electrical / mechanical properties, An example of surface modification has also been reported.

As described in the above-mentioned prior art, in order to produce the most optimized organic / inorganic hybrid material, it is preferable to synthesize an oligomer for surface modification specific to the organic group. For example, in the case of an amide-imide series polymer such as polyamide, polyimide or polyamideimide, an amide having nitrogen (N) element, a low molecular weight And then the resulting oligomer is chemically bonded to the silica particles to produce an organic nanohybrid resin.

The nitrogen-containing oligomer has a longer molecular length than a conventional silane coupling agent, but has a brittle property because it has a smaller molecular weight than a polymeric resin as an organic material. Therefore, when such an oligomer is modified with silicone, the flexibility is further increased, thereby minimizing the occurrence of cracks during external impact at the polymer / silica interface. In the case of modifying the surface of silica with flexible oligomers containing silicon, the mechanical energy dispersion effect due to the deformation of the oligomer is likely to be caused by the mechanical energy due to the external impact. As a result, it is expected that the durability due to the mechanical deformation of the inorganic or organic nanohybrid material will be greatly increased.

Korean Patent Registration No. 10-0945198 Korea Patent Office Registration No. 10-1604444

Accordingly, an object of the present invention is to provide an organic / inorganic nanohybrid coating, a resin, and a method for producing the same, which have improved flexibility, adhesiveness, and impact resistance through silica surface modification using an oligomer modified with silicone.

The above-mentioned object is achieved by a method of manufacturing a silicon-modified oligomer comprising the steps of: preparing a silicon-modified oligomer containing a nitrogen element; Protecting one end of the silicon-modified oligomer with a protective group; Mixing the surface-treated silica nanoparticles with the silicone-modified oligomer to obtain silica nanoparticles surface-modified with the silicone-modified oligomer; And mixing the silica nanoparticles surface-modified with the silicone-modified oligomer with a polymer comprising a nitrogen element, wherein the silicone-modified oligomer comprises a first monomer having at least one of an isocyanate and an amine group at its terminal, Wherein the first monomer and the second monomer are condensation-polymerized in the presence of a silicone monomer or a silicone oligomer, wherein the second monomer is at least one selected from the group consisting of silicon monomers, silicone monomers, Wherein the reaction product is obtained by using at least one of a first reactant, a second reactant and a silicon second reactant. The present invention is also directed to a method for producing an organic / inorganic hybrid nano hybrid coating comprising silica nanoparticles surface-modified with a silicone modified oligomer.

The organic solvent may be at least one selected from the group consisting of N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, DMAc, , And a mixture thereof. In addition, low polarity solvents such as toluene, benzene, xylene, and cyclohexane may be used together to improve the solubility of the silicone oligomer having high hydrophobicity.

The surface-treated silica nanoparticles may be prepared by: preparing silica nanoparticles using a sol-gel method; Surface-treating the silica nanoparticles by introducing a reactor to the surface; Removing the water, the alcohol solvent and the catalyst to obtain the surface-treated silica nanoparticles in a dispersed state in the organic solvent, wherein the step of preparing the silica nanoparticles comprises reacting a trivalent alkoxysilane or tetravalent alkoxysilane Is added to a solvent and stirred at 20 to 80 ° C. After adding distilled water and a catalyst thereto, the mixture is stirred and reacted until a solid content of 80% or more of reaction conversion is obtained. The treating step may be carried out using a silane having a functional group containing at least one of amine, acid anhydride, epoxide, isocyanate, thiol, and hydroxy groups It is preferable to introduce the reactor.

At least one of the first reactant and the second reactant may be represented by the following general formula (2) in the process of reacting the first reactant and the second reactant to produce an oligomer having an amideimide group, Wherein the first reactant or the second reactant is used to obtain a silicone-modified oligomer represented by the following formula (3): wherein R 1, R 2, R 3, R 4, R 5, Way.

≪ Formula 1 >

Here, n is the number of repeating units (degree of polymerization) representing the molecular weight of the compound, Y and Z are protecting groups, and AM and IM are amide groups and imide groups, respectively.

(2)

Here, m is an integer ranging from 1 to 20 representing a silicon (SO) repeating unit, and X represents a terminal group corresponding to the first reactant and the second reactant.

(3)

Herein, n is the number of repeating units (degree of polymerization) representing the molecular weight of the silicone-modified oligomer comprising silicon-amide-imide and is an integer in the range of 3 to 30, and f is a ratio of silicon (SO) .

Wherein the protecting group is selected from the group consisting of phthalic anhydride, maleic anhydride, succinic anhydride, phenyl isocyanate, naphthyl isocyanate, 3-methyl The nitrogen-containing polymer is preferably selected from the group consisting of 3-methylpentyl amine, aniline, naphthylamine, and mixtures thereof. The polymer comprising the nitrogen element may be selected from the group consisting of polyamide, polyimide, (polyimide) or polyamideimide (polyamideimide).

The above-mentioned object is achieved by a method of manufacturing a semiconductor device comprising: a polymer containing a nitrogen element; Modified silica nanoparticles comprising a silicon-modified oligomer having at least one selected from the group consisting of an amide group, an imide group, an amide imide group, and a mixture thereof and having a polymerization degree of from 3 to 30, The oligomer is obtained by condensation polymerization of a first monomer having at least one of an isocyanate and an amine group at its terminal and a second monomer having at least one of an acid anhydride, a carboxylic acid and a carboxylic acid chloride at the terminal thereof in an organic solvent , Wherein the first monomer and the second monomer are obtained by using at least one of a silicon first reactant and a silicon second reactant composed of a silicon monomer or a silicon oligomer and a silica modified with a silicon modified oligomer By organic or inorganic nano hybrid coatings containing nanoparticles It is achieved.

Here, the nitrogen-containing polymer may be polyamide, polyimide or polyamideimide series.

The above-mentioned object is also achieved by a method for producing a silicon-modified oligomer comprising the steps of: preparing a silicon-modified oligomer containing a nitrogen element; Protecting one end of the silicon-modified oligomer with a protective group; Mixing the surface-treated silica nanoparticles with the silicone-modified oligomer to obtain silica nanoparticles surface-modified with the silicone-modified oligomer; And mixing the silica nanoparticles surface-modified with the silicone-modified oligomer with a polymer comprising a nitrogen element, wherein the silicone-modified oligomer comprises a first monomer having at least one of an isocyanate and an amine group at its terminal, Wherein the first monomer and the second monomer are condensation-polymerized in the presence of a silicone monomer or a silicone oligomer, wherein the second monomer is at least one selected from the group consisting of silicon monomers, silicone monomers, Wherein the reaction product is obtained by using at least one of a first reactant, a second reactant and a silicon second reactant. The present invention also provides a method for producing an organic / inorganic hybrid nanohybrid resin.

As well as a polymer comprising a nitrogen element; Modified silica nanoparticles comprising a silicon-modified oligomer having at least one selected from the group consisting of an amide group, an imide group, an amide imide group, and a mixture thereof and having a polymerization degree of from 3 to 30, The oligomer is obtained by condensation polymerization of a first monomer having at least one of an isocyanate and an amine group at its terminal and a second monomer having at least one of an acid anhydride, a carboxylic acid and a carboxylic acid chloride at the terminal thereof in an organic solvent , Wherein the first monomer and the second monomer are obtained by using at least one of a silicon first reactant and a silicon second reactant composed of a silicon monomer or a silicon oligomer and a silica modified with a silicon modified oligomer Even with organic or inorganic nano hybrid resin containing nanoparticles The above object is achieved.

According to the structure of the present invention described above, the organic or inorganic nano hybrid coating agent and the resin prepared by including the silica nanoparticles surface-modified with the silicone modified oligomer have a high degree of chain entanglement between the oligomer and the polymer, And the adhesive property and the impact resistance property are improved by the increased flexibility.

1 is a flowchart of an organic / inorganic nano hybrid coating agent and a resin manufacturing method according to an embodiment of the present invention,
2 is a view showing a method of confirming physical properties of an organic nano hybrid coating agent and a resin,
Fig. 3 is a photograph showing the physical properties of the organic / inorganic nano hybrid coating agent and the resin as confirmed by Fig.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an organic / inorganic nano hybrid coating material containing silica nanoparticles modified with a silicone modified oligomer according to an embodiment of the present invention will be described in detail.

First, as shown in FIG. 1, a silicon-modified oligomer containing a nitrogen element is prepared (S1).

The silicone modified oligomer is prepared to have a degree of polymerization of 3 to 30. If the polymerization degree of oligomer is less than 3, it is difficult to expect chain entanglement between oligomers or oligomers and polymers. If the degree of polymerization exceeds 30, molecular weight of oligomers becomes about molecular weight. It is not easy to use for the surface modification of the silica sol and it is difficult to find a terminal because it is composed of a long chain, so that the bonding reaction with silica sol is not easy.

The oligomer is preferably selected from the group consisting of an amide group, an imide group, an amideimide group, and a mixture thereof. The oligomer is preferably selected from the group consisting of a nitrogen-containing functional group the functional group is preferably selected from the group consisting of an isocyanate group, an amine group and a mixture thereof.

As the method of preparing the oligomer, there is a method in which a first monomer having at least one of terminal isocyanate and amine group and a second monomer having terminal at least one of acid anhydride, carboxylic acid, In the condensation polymerization reaction in a solvent, the first monomer and the second monomer are obtained by using at least one of a silicon first reactant and a silicon second reactant, which are silicon monomers or silicon oligomers.

The organic solvent in which the condensation polymerization reaction is carried out is selected from the group consisting of N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide , DMAc), and a mixture thereof. In addition, low polarity solvents such as toluene, benzene, xylene, and cyclohexane may be used together to improve the solubility of the silicone oligomer having high hydrophobicity.

In the case of an oligomer having an amide group, a first reactant having a diisocyanate group is prepared, and a second reactant having a dicarboxylic acid is condensed in an organic solvent. It is prepared by condensation polymerization reaction. The first reactant may use a diamine group instead of the diisocyanate group, and the second reactant may use a dicarboxylic acid chloride instead of the dicarboxylic acid.

In the case of an oligomer having an imide group, a first reaction product having a diamine group and a second reaction product having an acid anhydride may be prepared through a condensation polymerization reaction in a solvent, or a first reaction with a diisocyanate And a second reactant having a sieve and an anhydride can be produced by condensation polymerization.

The synthesis of an oligomer having an amideimide group can be prepared from a first reactant having a diisocyanate group and a second reactant having both ends made of an acid anhydride and a carboxylic acid. Here, a first reactant having a diamine group instead of a diisocyanate can be used, and a dicarboxylic acid chloride instead of a dicarboxylic acid can be used as the second reactant.

It is preferable to use methylene diphenyl diisocyanate, toluene diisocyanate and hexamethylenediisocyanate as the diisocyanate group, and the dicarboxylic acid is preferably naphthalene 1,8-dicarboxylic acid (naphtanlene 1, 8-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, 2,2'-bipyridine 4,4'-dicarboxylic acid, pyrrolidine-2,4-dicarboxylic acid and 4,5-imidazoledicarboxylic acid. .

The diamine group may also be selected from the group consisting of phenylene diamine, methylene diamine, ethylene diamine, 6-methyl-1,3,5-triazine-2,4-diamine, 3,5-triazine-2,4-diamine, and the dicarboxylic acid chloride is pyridine-2,5-dicarboxylic acid chloride, diphenyl-4,4 ' Diphenyl-4,4'-dicarboxylic acid chloride is preferably used. The anhydride is preferably pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride (4 , 4'-oxydiphtalic dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic dianhydride are preferably used.

Here, in order to produce a silicone-modified oligomer, at least one of the first reactant and the second reactant is a silicon-containing reactant as shown in Formula 1, and the silicon-modified oligomer produced through the silicon- . As the first reactant, a silicone monomer or a silicone oligomer having an isocyanate or an amine group at the terminal may be used, and as the second reactant, a silicone monomer or a silicone oligomer having a terminal acid anhydride, a carboxylic acid or a carboxylic acid chloride may be used have.

Wherein at least one of the first reactant and the second reactant is represented by the following general formula (2), wherein the first reactant and the second reactant react to form an oligomer having an amideimide group, A silicone modified oligomer represented by the following general formula (3) can be obtained by using the first reactant or the second reactant.

≪ Formula 1 >

Here, n is the number of repeating units (degree of polymerization) representing the molecular weight of the compound, Y and Z are protecting groups, and AM and IM are amide groups and imide groups, respectively.

(2)

Here, m is an integer ranging from 1 to 20 representing a silicon (SO) repeating unit, and X represents a terminal group corresponding to the first reactant and the second reactant.

(3)

Herein, n is the number of repeating units (degree of polymerization) representing the molecular weight of the silicone-modified oligomer comprising silicon-amide-imide and is an integer in the range of 3 to 30, and f is a ratio of silicon (SO) .

The modifying silicone material formed through the first reactant and the second reactant is preferably an oligomer rather than a monomer in terms of imparting flexibility, and it is most preferable that the molecular weight of the silicone oligomer is 1 to 20, Do. When m is 20 or more, the size of the oligomer having a nitrogen-denatured nitrogen atom becomes too large, and the hydrophobicity becomes too large, and the compatibility with the organic polymer resin may be deteriorated. Such a modifying silicone oligomer preferably replaces 1 to 50 mol% of the existing first reactant and second reactant, but there is no particular limitation so long as compatibility with the organic polymer resin is ensured.

The organic solvent may be an organic solvent capable of dissolving the first reactant and the second reactant, such as N-methylpyrrolidone, N, N-dimethylformamide (DMF), N, N (N, N-dimethylacetamide, DMAc), and a mixture thereof. In addition, various solvents capable of dissolving the first and second reactants may be used. The condensation polymerization reaction temperature of the first reactant and the second reactant is preferably 50 to 150 ° C.

In the case of producing a silicone-modified oligomer modified with silicone using a silicone oligomer, the above-mentioned solvent may be used. In order to improve the solubility of the silicone monomer having a high hydrophobicity, a low polarity solvent such as toluene, benzene, xylene, or cyclohexane may be used together.

One end of the oligomer is protected with a protecting group (S2).

The oligomer produced in step S1 has an active group at both ends. When a reactor is present at both ends, the silica nanoparticles bind to both ends of the oligomer in the subsequent step, and two silica nanoparticles Surface modification problems arise. When a plurality of silica nanoparticles are stuck to one another in this manner, the silica nanoparticles aggregate with each other, resulting in poor dispersibility and storage stability. Thus, one end of the oligomer is protected using a protective group, which allows one oligos to bind to one of the silica sols.

The protecting group is selected from the group consisting of aliphatic, cycloaliphatic, aromatic, and mixtures thereof that do not react with the materials used in the subsequent steps to protect the reactor. Such protecting groups may be selected from the group consisting of phthalic anhydride, maleic anhydride, succinic anhydride, phenyl isocyanate, naphthyl isocyanate, 3-methylpentyl 3-methylpentyl amine, aniline, and naphthylamine. In addition, a substance that does not react with the terminal may be used.

The terminal of the oligomer which is not protected with a protecting group includes a reactor such as an isocyanate group, an amine group, an acid anhydride group, a hydroxyl group, an amide group, an epoxy group, a carboxylic acid, a carboxylic acid chloride, Reaction.

The silica nanoparticles bound to the oligomer are obtained through the following S1 'to S3' steps using a sol-gel method.

First, silica nanoparticles are prepared using a sol-gel method (S1 ').

The silica nanoparticles using the sol-gel method are prepared using silane as a starting material, and the silane for preparing silica can be prepared by using trivalent alkoxysilane or tetravalent alkoxysilane. Wherein the trivalent alkoxysilane is selected from the group consisting of trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, methyltrimethoxy But are not limited to, silane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and mixtures thereof. And tetraalkoxysilane is preferably selected from the group consisting of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetraethoxysilane, tetraethoxysilane, Tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, and a mixture thereof. Preferably selected from a group but are not limited thereto.

The silica nanoparticles are prepared by adding the corresponding silane to an alcohol solvent, stirring the mixture at 20 to 80 ° C, adding distilled water and a catalyst thereto, and stirring the mixture again until a solid content of 80% or more is obtained . The alcohol solvent used herein may be methanol, ethanol, propanol, isopropanol, or butanol, which can dissolve silane and silica. The catalyst may be ammonium hydroxide, It is preferable to use a basic catalyst such as ammonium chloride, methylamine or the like, which is diluted in distilled water and added to the solvent.

The surface of the silica nanoparticles is treated (S2 ').

In step S2, the silica is surface-treated by introducing a reactor to the surface of the silica nanoparticles for chemical bonding between the oligomer and the silica nanoparticle with one terminal group protected. The silane used in the surface treatment may be a silane having a functional group containing at least one of an amine, an acid anhydride, an epoxide, an isocyanate, a thiol and a hydroxy group Lt; / RTI >

Here, the silane having a functional group may be selected from the group consisting of N- (beta-aminoethyl) -gammaaminopropylmethyldimethoxysilane (N- (beta-aminoethyl) gammaaminopropylmethyldimethoxysilane), aminopropyltrimethoxysilane, But are not limited to, aminopropyl triethoxysilane, glycidoxypropyl trimethoxysilane, glycidoxypropyl triethoxysilane, gamma-isocyanatopropyl trimethoxysilane, But are not limited to, gamma-isocyanatopropyl triethoxysilane, hydroxymethyl triethoxysilane, hydroxyethylaminopropyl triethoxysilane, hydroxyethyl-N -Hydroxyethyl-N-methylaminopropyl trimethoxysilane, 3-triethoxysilylpropyl From the group consisting of 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and mixtures thereof. Is preferably selected.

In the method of surface-treating silica nanoparticles, a silane containing a functional group is dissolved in a solvent, which is then injected and stirred into a silica mixture. For the surface treatment of silica nanoparticles, in addition to the basic catalyst, acetic acid, formic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid ) Can also be used.

The water, the alcohol solvent and the catalyst are removed to obtain surface-treated silica nanoparticles dispersed in the organic solvent (S3 ').

Removing the water, the alcohol solvent and the catalyst from the surface-treated silica nanoparticles after the surface treatment of the silica nanoparticles, wherein the water, the alcohol solvent and the catalyst are removed by evaporation. In addition to the evaporation method, it can be removed by freeze drying. This method can remove moisture, catalyst and alcohol solvent.

In order to prepare the silica nanoparticles and then subject them to surface treatment as in the present invention, an acid or base catalyst and distilled water should be used. If the silica nanoparticles are surface-treated with a catalyst and distilled water in the state where oligomers are mixed as in the prior art without surface treatment of the silica nanoparticles separately from the oligomer as in the present invention, the oligomer chain is broken or denatured . Therefore, it is most preferable that the silica nanoparticles are separately surface-treated (S2 ') as in the present invention, and the water, the alcohol solvent and the catalyst are removed (S3') to prepare the silica nanoparticles dispersed in the organic solvent.

To prepare silica nanoparticles surface-modified with an oligomer (S3).

The organic solvent-dispersed silica nanoparticles surface-treated through the silane in steps S1 'to S3' are mixed and stirred with the silicon-modified oligomer prepared in step S2 to prepare the surface-modified silica nanoparticles with the oligomer.

The silica nanoparticles and the silicone modified oligomer are reacted by stirring at 20 to 200 ° C. When the reaction temperature is lower than 20 ° C., the reaction takes a long time. When the temperature exceeds 200 ° C., the silica nanoparticles or the silicone modified oligomer Lt; / RTI > The content of the oligomer is 5 to 50 parts by weight based on 100 parts by weight of the silica solids. Through such a reaction, oligomer chains are bonded to the surface-treated silica nanoparticles to obtain silica nanoparticles surface-modified with oligomers.

The silica nanoparticles are mixed with the polymer (S4).

The silica nanoparticles surface-modified with a silicon-modified oligomer containing a nitrogen element are mixed with a polymer containing a nitrogen element to prepare an organic nanohybrid coating agent or resin. Here, the polymer containing the nitrogen element uses a polyamide, polyimide or polyamideimide series having a structure similar to an oligomer containing a nitrogen element. The mixing ratio of the polymer and the silica nanoparticles is preferably 10 to 30 parts by weight of the silica nanoparticles to 100 parts by weight of the polymer.

Examples of the method for producing such an organic or inorganic nano hybrid coating agent or resin are as follows.

<Examples>

, 11 parts by weight of trimellitic anhydride, 15 parts by weight of methylene diphenyl diisocyanate and 26 parts by weight of carboxylic acid terminal silicone (molecular weight: 4600 g / mol) were added to N-methylpyrrolidone (N -methyl pyrrolidone), and reacted at 80 ° C. 1.5 parts by weight of phthalic anhydride was further added thereto, followed by sufficient reaction at the same temperature. Thereafter, the temperature was raised to 120 ° C to terminate the reaction, thereby producing a modified silicone oligomer containing an amideimide group.

Silica nanoparticles were synthesized from triethoxysilane (TEOS) by sol - gel reaction. To this end, 100 parts by weight of TEOS and 330 parts by weight of methanol were mixed and stirred at 60 DEG C for about 30 minutes. Then, an aqueous solution containing 20 parts by weight of distilled water and 10 parts by weight of ammonia water was added to react. Thereafter, the reaction temperature was maintained at 60 占 폚 until a solid content of 80% or more of reaction conversion was obtained to obtain high purity nano-silica sol.

Phenyltrimethoxysilane and 3-aminopropyltriethoxysilane were added to the high-purity silica sol in an amount of 15 parts by weight and 2.5 parts by weight, respectively, based on 100 parts by weight of the silica solids, and N-methylpyrrolidone ( N-methylpyrrolidone) solution, which was then injected into the silica sol and stirred for 20 hours. Then, residual water, ammonia and alcohol were removed using a rotary evaporator to prepare organically dispersed silica nanoparticles.

The synthesized silicone modified oligomer solution was mixed in an amount of 5 to 20 parts by weight based on 100 parts by weight of solids of the organic dispersed silica nanoparticles and allowed to react for one day to prepare oligomer-bound silica nanoparticles. The modified silicone amide imide oligomer-bonded silica nanoparticles were mixed with a polyamideimide resin so that the amount of silica was 15 parts by weight based on 100 parts by weight of resin solids, and the mixture was stirred for one day to obtain a polyamideimide / silica nano- To prepare a hybrid resin. A PAI / silica nanohybrid coating was finally prepared by coating and drying a polyamideimide / silica nanohybrid resin on the surface of a copper sheet (0.3 mm thick).

The adhesion of PAI / silica nanohybrid coatings prepared on copper sheet was evaluated by 180 ° bending test. For this purpose, as shown in FIG. 2, a copper sheet coated with a coating film was inserted between stainless steel plates having a spacing of 1.0 mm, then a sufficient load was applied in the vertical direction, and a crack occurred on the folded surface And the adhesion between the coating film and the copper sheet was evaluated. The average crack occurrence was analyzed by observing 10 images in consideration of the variation of crack occurrence.

As shown in FIG. 3, when the silica nanoparticles surface-treated with silane were used, the frequency of occurrence of cracks was large while the frequency of occurrence of cracks was significantly reduced when silica-modified oligomer-bonded silica nanoparticles were used. It was confirmed that the adhesive strength was greatly improved. In addition, when the oligomer is treated with 5 or 10 pt of silica solids, 5 pt shows an excellent adhesive force as compared with 10 pt. This means that it is preferable to use only as necessary for the surface treatment of silica in the use of the silicone modified oligomer prepared in the present invention Able to know. It is considered that when the polymer is mixed with the bulk polymer in excessive use, the compatibility with the polymer resin is lowered and the self-strength is lowered.

Generally, inorganic nanoparticles including silica are surface-modified by mixing inorganic nanoparticles with organic materials such as polymers to prevent deterioration of dispersibility due to a large difference in surface characteristics and to improve physical properties through interfacial bonding . In the present invention, an oligomer having a chemical structure similar to that of an organic polymer to be mixed in addition to a conventional alkoxysilane as a silica surface modifying material is prepared and chemically bonded to silica particles, thereby developing a more specific silica surface modifying method. In addition, the oligomer was denatured by silicone with high flexibility, so as to minimize the destruction due to deformation at the interface between silica and the surrounding environment. In addition, because silicon is a hydrophobic material with low surface energy, it has an advantage in that it can control the surface energy of the finally polymer film to be coated.

Claims (11)

1. A method for manufacturing an organic / inorganic nano hybrid coating material comprising silica nanoparticles surface-modified with a silicone-modified oligomer,
Preparing a silicon-modified oligomer comprising a nitrogen element;
Protecting one end of the silicon-modified oligomer with a protective group;
Mixing the surface-treated silica nanoparticles with the silicone-modified oligomer to obtain silica nanoparticles surface-modified with the silicone-modified oligomer;
And mixing the silica nanoparticles surface-modified with the silicon-modified oligomer with a polymer comprising a nitrogen element,
The silicone-modified oligomer is obtained by reacting a first monomer having a terminal at least one of isocyanate and amine groups and a second monomer having at least one terminal of an acid anhydride, a carboxylic acid or a carboxylic acid chloride in an organic solvent Wherein the first monomer and the second monomer are obtained by using at least one of a silicon first reactant and a silicon second reactant comprising a silicon monomer or a silicon oligomer, Wherein the modified nanohybrid coating comprises modified silica nanoparticles. The method according to claim 1,
The above-mentioned surface-treated silica nanoparticles can be obtained by,
Preparing silica nanoparticles using a sol-gel method;
Surface-treating the silica nanoparticles by introducing a reactor to the surface;
And removing the water, the alcohol solvent, and the catalyst to obtain the surface-treated silica nanoparticles in a dispersed state in the organic solvent. The method of claim 1, wherein the organic nano- &Lt; / RTI &gt; 3. The method of claim 2,
The step of preparing the silica nanoparticles comprises:
Trivalent alkoxysilane or tetraalkoxysilane is added to the solvent, followed by stirring at 20 to 80 ° C. Distilled water and the catalyst are added thereto, and the mixture is stirred again until the solid content of the reaction conversion ratio of 80% or more is obtained Wherein the silica nanoparticles are surface-modified with a silicone-modified oligomer. 3. The method of claim 2,
The step of surface-treating the silica nanoparticles comprises:
Introducing the reactor using a silane having a functional group containing at least one of amine, acid anhydride, epoxide, isocyanate, thiol, and hydroxy groups Wherein the silica nanoparticles are surface-modified with a silicone-modified oligomer. The method according to claim 1,
Wherein at least one of the first reactant and the second reactant is represented by the following general formula (2), wherein the first reactant and the second reactant react to form an oligomer having an amideimide group, Wherein the first reactant or the second reactant is used to obtain a silicone-modified oligomer represented by the following formula (3).
&Lt; Formula 1 >

Here, n is the number of repeating units (degree of polymerization) representing the molecular weight of the compound, Y and Z are protecting groups, and AM and IM are amide groups and imide groups, respectively.
(2)

Here, m is an integer ranging from 1 to 20 representing a silicon (SO) repeating unit, and X represents a terminal group corresponding to the first reactant and the second reactant.
(3)

Herein, n is the number of repeating units (degree of polymerization) representing the molecular weight of the silicone-modified oligomer comprising silicon-amide-imide and is an integer in the range of 3 to 30, and f is a ratio of silicon (SO) . The method according to claim 1,
Wherein the protecting group is selected from the group consisting of phthalic anhydride, maleic anhydride, succinic anhydride, phenyl isocyanate, naphthyl isocyanate, 3-methyl Wherein the organic nanoparticle comprises a silica nanoparticle surface-modified with a silicon-modified oligomer, wherein the inorganic nanohybrid is selected from the group consisting of 3-methylpentyl amine, aniline, naphthylamine, &Lt; / RTI &gt; The method according to claim 1,
Wherein the nitrogen-containing polymer is a polyamide, polyimide or polyamideimide series organic or inorganic nano hybrid including silica nanoparticles surface-modified with a silicon-modified oligomer. &Lt; / RTI &gt; An organic or inorganic nano hybrid coating comprising silica nanoparticles surface-modified with a silicone modified oligomer,
A polymer comprising a nitrogen element;
A silica nanoparticle surface-modified with a silicon-modified oligomer having at least one selected from the group consisting of an amide group, an imide group, an amide imide group and a mixture thereof, and a nitrogen element having a degree of polymerization of 3 to 30,
The silicone-modified oligomer is obtained by reacting a first monomer having a terminal at least one of isocyanate and amine groups and a second monomer having at least one terminal of an acid anhydride, a carboxylic acid or a carboxylic acid chloride in an organic solvent Wherein the first monomer and the second monomer are obtained by using at least one of a silicon first reactant and a silicon second reactant comprising a silicon monomer or a silicon oligomer, Wherein the modified nanohybrid coating comprises modified silica nanoparticles. 9. The method of claim 8,
Wherein the nitrogen-containing polymer is a polyamide, polyimide or polyamideimide series organic or inorganic nano hybrid including silica nanoparticles surface-modified with a silicon-modified oligomer. Coating agent. A method for producing an organic / inorganic hybrid nanohybrid resin comprising silica nanoparticles surface-modified with a silicone-modified oligomer,
Preparing a silicon-modified oligomer comprising a nitrogen element;
Protecting one end of the silicon-modified oligomer with a protective group;
Mixing the surface-treated silica nanoparticles with the silicone-modified oligomer to obtain silica nanoparticles surface-modified with the silicone-modified oligomer;
And mixing the silica nanoparticles surface-modified with the silicon-modified oligomer with a polymer comprising a nitrogen element,
The silicone-modified oligomer is obtained by reacting a first monomer having at least one of an isocyanate and an amine group at its terminal and a second monomer having at least one of an acid anhydride, a carboxylic acid and a carboxylate at the terminal thereof in an organic solvent Wherein the first monomer and the second monomer are obtained by using at least one of a silicon first reactant and a silicon second reactant comprising a silicon monomer or a silicon oligomer, Modified nanohybrid resin containing modified silica nanoparticles. An organic / inorganic nano hybrid resin comprising silica nanoparticles surface-modified with a silicone-modified oligomer,
A polymer comprising a nitrogen element;
A silica nanoparticle surface-modified with a silicon-modified oligomer having at least one selected from the group consisting of an amide group, an imide group, an amide imide group and a mixture thereof, and a nitrogen element having a degree of polymerization of 3 to 30,
The silicone-modified oligomer is obtained by reacting a first monomer having at least one of an isocyanate and an amine group at its terminal and a second monomer having at least one of an acid anhydride, a carboxylic acid and a carboxylate at the terminal thereof in an organic solvent Wherein the first monomer and the second monomer are obtained by using at least one of a silicon first reactant and a silicon second reactant comprising a silicon monomer or a silicon oligomer, Wherein the modified nanohybrid resin contains modified silica nanoparticles.

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