JP2008074699A - Method for manufacturing high dielectric-constant inorganic/organic hybrid film containing crystalline barium titanate nanoparticle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a high dielectric-constant inorganic/organic hybrid containing crystalline barium titanate nanoparticles, and to provide an inorganic/organic barium titanate hybrid manufactured by the method and a high dielectric film having flexibility. <P>SOLUTION: A step of manufacturing a medium for the inorganic/organic hybrid through a hydrolysis reaction of a silane compound by adding acid and an ion-exchanged water to the silane compound, a step of dispersing the crystalline barium titanate nanoparticle manufactured by another method to the manufactured medium and a step of forming an inorganic/organic hybrid coating film wherein the barium titanate is dispersed by applying the medium on a flexible substrate and curing by heat or optical energy after drying are included. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a non-organic hybrid having a high dielectric constant, and a non-organic hybrid produced therefrom, and more specifically, crystalline barium titanate nanoparticles expected to be used in embedded capacitors The present invention relates to a method for producing a non-organic hybrid containing a non-organic hybrid and a non-organic hybrid produced therefrom.

  Embedded capacitors have been developed to reduce assembly costs and improve electrical performance from traditional surface mounting single capacitors. In order to manufacture a capacitor embedded in a flexible substrate, the dielectric constant has a high capacitance value and a low capacitance tolerance, which makes it possible to coat organic substrates with flexibility and processability. There is a demand for materials that are superior but have low manufacturing costs.

  Recently, non / organic hybrid materials are capable of combining inorganic particles having a high dielectric constant with organic components having excellent flexibility and processability, and are attracting attention as embedded capacitor materials for electronic circuits using organic substrates. In particular, various methods for producing nanocomposites using barium titanate having a high dielectric constant and a polymer have been tried. In order to increase the dielectric constant of barium titanate-polymer composites, it is necessary to insert as much barium titanate as possible into the polymer, but between the inorganic barium titanate and the organic polymer. Due to the large difference in the interfacial energy, it is very difficult to produce a composite having excellent uniformity, and the processability and flexibility of the composite are low. Therefore, although some attempts have been made to generate high-dielectric inorganic substances such as barium titanate in the polymer medium in-situ, organic polymers have low thermal stability and thus are There is a limit to producing high dielectric inorganic particles with excellent crystallinity by applying energy, and it is very difficult to manufacture at low prices (T. Yogo, T. Yamamoto, W. Sakamoto, SI Hirano, J. Mater Res., 2004, 19, 3290). Therefore, after first producing crystalline high dielectric barium titanate nanoparticles, attempts have been made to produce a non-organic composite material by dispersing and mixing in an organic polymer medium at a high concentration (H. Hsiang, K. -Y Lin, F. -S. Yen, C. -Y. Hwang, J. Mater. Sci., 2001, 36, 3809; Y. Rao and CP Wong, J. Appl. Polym. Sci., 2004, 92, 2228). However, the polymer composite produced by this method has a low dielectric constant of 60 or less even when barium titanate is intruded in an amount of 60% by volume or more. There is a problem that most of the advantages, ie, flexibility and workability are lost.

  Considering the current technical requirements for electronic components and the increasing demand for nanoparticles based on barium titanate, the high dispersibility, flexibility and processability of inorganic particles as organic media are of paramount importance. There must be.

  In an attempt to overcome such problems, a technique using epoxy and / or X7R in an organic medium has been reported (DH Kuo, C). -C. Chang, T. -Y. Su, W. -K. Wang, B. -Y. Lin, J. Eur. Ceram. Soc. 21 (2001) 1171; DH Kuo, C. -C. Chang T. -Y. Su, W. -K. Wang, B. -Y. Lin, Mater. Chem. Phys. 85 (2004) 20). However, such a method has a disadvantage that a high curing temperature is required. Second, to improve the dispersibility of crystalline barium titanate nanoparticles in organic media, the surface of the nanoparticles is modified with organic additives (ZG Shen, JF Chen, HK Zou, J. Yun, J. Colloid Interf. Sci. 275 (2004) 158; X. Wu, L. Zou, S. Yang, D. Wang, J. Colloid Interf. Sci. 239 (2001) 369; PD Cozzoli, A. Kornowski H. Weller, J. Am. Chem. Soc. 125 (2003) 14539), a method for producing monodispersed barium titanate using a Ba-Ti-alkoxide precursor (S. O'Brien, L. There have been various attempts such as Brus, CB Murray, J. Am. Chem. Soc. 123 (2001) 1208), but further improvement is necessary in terms of dispersibility and dielectric constant.

  Accordingly, the present invention provides a method for producing a barium / organic barium titanate hybrid having a relatively low content of crystalline barium titanate nanoparticles and having a high dielectric constant compared to existing known methods. More specifically, crystalline barium titanate nanoparticles having a high dispersibility in an organic solvent, and a silane compound having excellent surface affinity with the barium titanate nanoparticles are used as a medium. It is an object of the present invention to provide a method for producing a no-organic barium titanate hybrid in which is uniformly dispersed on a medium.

  Another object of the present invention is a no / organic barium titanate hybrid produced by the above production method, and a no / organic titanate excellent in flexibility and dielectric properties produced by coating, drying and curing the same. The object is to provide a barium hybrid dielectric film.

  The present invention relates to a method for producing a no / organic barium titanate hybrid and a no / organic barium titanate hybrid dielectric film produced therefrom.

The method for producing a no / organic barium titanate hybrid according to the present invention includes the following steps.
1) A step of adding an acid to one or more silane compound solutions represented by the following chemical formula 1 and heating to produce a medium for no / organic hybrid; and 2) crystalline titanic acid in the medium for no / organic hybrid; A method for producing a no / organic barium titanate hybrid comprising: dispersing barium nanoparticles to produce a no / organic barium titanate hybrid;
<Chemical Formula 1>
(R ¹ ) _n Si (OR ² ) _4-n
Wherein n is an integer of 1 to 3; R ¹ is a vinyl group or an alkyl group having 1 to 10 carbon atoms having a reactive group, and the reactive group is a (meth) acrylate group, a vinyl group or An epoxy group, wherein the alkyl group contains a heteroatom selected from N, O or S; R ² is alkyl or alkenyl having 1 to 5 carbon atoms.)

  The step 1) further includes a step of removing the acid used as the hydrolysis catalyst by a solvent extraction method, and distilling the solvent under reduced pressure to obtain a medium for non / organic hybrid. After the step 2), the non / organic titanium is obtained. The method further includes coating the barium acid hybrid on the substrate and then drying and curing to form a film.

  The present invention also provides a non-organic hybrid produced by the method for producing a non-organic barium titanate hybrid as described above, and a high dielectric constant produced by coating the substrate on a substrate, followed by drying and curing. A flexible dielectric film is provided.

  Hereinafter, the present invention will be described in more detail.

  In this case, unless otherwise defined in the technical and scientific terms used, it has the meaning normally known by those having ordinary knowledge in the technical field to which the present invention belongs. In addition, the repeated description with respect to the technical structure and effect | action same as the past is omitted.

The present invention provides a method for producing a no / organic barium titanate hybrid comprising the following steps.
1) A step of adding an acid to one or more silane compound solutions represented by the following chemical formula 1 and heating to produce a medium for no / organic hybrid; and 2) crystalline titanic acid in the medium for no / organic hybrid; A method for producing a no / organic barium titanate hybrid comprising: dispersing barium nanoparticles to produce a no / organic barium titanate hybrid;
<Chemical Formula 1>
(R ¹ ) _n Si (OR ² ) _4-n
Wherein n is an integer of 1 to 3; R ¹ is a vinyl group or an alkyl group having 1 to 10 carbon atoms having a reactive group, and the reactive group is a (meth) acrylate group, a vinyl group or An epoxy group, wherein the alkyl group contains a heteroatom selected from N, O or S; R ² is alkyl or alkenyl having 1 to 5 carbon atoms.)

The method for producing a barium titanate hybrid according to the present invention uses the silane compound represented by Formula 1 as a non / organic hybrid material. The silane compound preferably has a vinyl group, a (meth) acrylate group or an epoxy group, and the other has a trialkoxy group, and includes silane compounds represented by the following chemical formulas 2 to 4.
<Chemical formula 2>
<Chemical formula 3>
<Chemical Formula 4>
(In the formulas 2 to 4, R ² is the same as defined in formula 1, R ³ is hydrogen or methyl, A is independently a chemical bond and alkylene having 1 to 10 carbon atoms. The alkylene contains an oxygen atom in the carbon chain.)

  Examples of the compound of Formula 1 include 3-methacryloyloxypropyl trimethoxysilane (MPTS), 3-glycidyloxypropyl trimethoxysilane (GPS), vinyl triisopro An example is vinyltriisopropenoxysilane (VTIPS). In particular, when a silane compound having an alkyl group substituted with a (meth) acrylate group or an epoxy group and a trialkoxy group is used in the silane compound, the flexibility of the organic / barium titanate hybrid and the barium titanate Dispersibility is the best and more desirable.

  The silane compound is dissolved in an organic solvent such as alcohol and manufactured as a solution, and then hydrolyzed by adding an acid. At this time, the hydrolysis reaction may be performed at room temperature, but it is desirable to heat the silane compound solution at 60 to 90 ° C. so that the hydrolysis reaction proceeds more smoothly.

  The added acid may be any acid selected from inorganic acids or organic acids, but when used in a high dielectric capacitor film, the current state of electrical brake down due to electrically conductive impurities is minimized. It is more desirable to use nitric acid, an inorganic acid, which can be easily removed from the hydrolyzed medium through a separate process and can be further easily removed at a low heat treatment temperature.

  The silane compound of Formula 1 forms a slightly viscous non-organic hybrid solvate by forming a network of hydroxyl groups and Si—O—Si in the hydrolysis and polycondensation reactions. Solvent using organic solvent such as toluene and distilled water to prevent gel formation of medium by nitric acid catalyst used in silane hydrolysis catalyst in the present invention and to minimize electric brake down of no / organic barium titanate dielectric film Nitric acid was removed from the produced medium by the displacement method. In other words, the hydrolyzed silane-based medium is dissolved in an organic solvent layer such as toluene, nitric acid is separated using the principle of being dissolved in distilled water, and finally the medium dissolved in toluene is removed by vacuum distillation. To obtain a medium for no / organic hybrid.

  From the step 2), crystalline / barium titanate nanoparticles prepared by a separate method are dispersed in the obtained medium to prepare a non-organic barium titanate hybrid type material.

The crystalline barium titanate nanoparticles or dispersion thereof according to the present invention is manufactured by the manufacturing method disclosed in Korean Patent Application No. 2006-0054304 filed by the present inventors. It is manufactured by the manufacturing method including these steps.
(A) a step of preparing a mixed solution by dissolving a titanium alkoxide and a diamine compound of the following chemical formula 5 in a solvent;
(B) adding the mixture to the aqueous barium hydroxide solution and then stirring to form barium titanate; and (c) separating the barium titanate.
<Chemical formula 5>
(In the formula, R is selected from alkylene groups having 2 to 8 carbon atoms.)

  The barium titanate crystalline nanoparticles produced by the above production method have the most excellent dispersibility in organic solvents because the diamine compound is bonded to the surface of the barium titanate nanoparticles.

  In the method for producing crystalline barium titanate nanoparticles, the molar ratio of the diamine compound to the titanium alkoxide is preferably 1 to 20, and more preferably 3 to 10 molar ratio. When the molar ratio of the diamine compound to the titanium alkoxide is less than 1, there is a possibility that amorphous barium titanate is mixed, and the effect of improving the dispersibility in the organic solvent is not large, and the molar ratio is 20 In the case where it exceeds 1, the effect of the uniformity and dispersibility of the particle size distribution due to the addition is slight, which may be economically disadvantageous. The diamine compound is preferably ethylene diamine (EDA) or propane diamine, and when ethylene diamine (EDA) or propane diamine is used, it is a 5-membered ring or a 6-membered ring. This is because the bonding is relatively stable and remains on the surface of the crystalline barium titanate.

  The medium in step 2) and the solution for dispersing crystalline barium titanate nanoparticles are alcohols such as methanol, ethanol and isopropyl alcohol, N, N-dimethylformamide (DMF), methyl isobutyl ketone (MIBK) or cyclohexanone (Cyclohexanone, It is desirable to use a polar organic solvent such as CHN) because of excellent dispersibility, and it is more desirable to use N, N-dimethylformamide (DMF) or methanol because of excellent dispersibility.

  It is well known that crystalline oxide nanoparticles, especially barium titanate nanoparticles synthesized at low temperatures and aqueous solutions, have a number of OH groups on the surface. In step 2), a Ti-O-Si network is formed by a condensation reaction between the OH groups present on the surface of the barium titanate nanoparticles and the siloxane groups present in the end groups of the silane-based medium produced from step 1). However, a barium titanate hybrid in which barium titanate is uniformly dispersed in a non / organic hybrid medium is formed.

  The content of crystalline barium titanate nanoparticles is 0.5 to 40.0% by weight (0.1 to 10.0% by volume) based on the total mass of barium titanate and a silane-based no / organic hybrid medium. What was made like this is desirable, and what is 1.0 to 30 weight% (0.5 to 7 volume%) is further more desirable. When the content is less than 0.5% by weight, the dielectric constant is low and undesirable, and when the content is more than 40% by weight, the uniformity of the dielectric film produced from the no / organic barium titanate hybrid Breaks or causes phase separation of barium titanate and no / organic hybrid, greatly reducing flexibility and damaging the advantages of the no / organic hybrid material.

  The step 2) includes a process for preparing a barium / organic barium titanate hybrid having different viscosities by partially removing the solvent in order to adjust the thickness of the coating film. After removing the solvent to have a viscosity that is compatible with a coating method such as spin coating and the production of the desired thick coating film, it is used to produce a hybrid dielectric film.

  A flexible dielectric film having a high dielectric constant is coated on a glass or plastic substrate with a specific viscosity-free / organic barium titanate hybrid prepared by the above method, and then dried and cured to produce a flexible dielectric film. To do. In the above, drying conditions are performed at a temperature of 100 to 120 ° C. for 0.5 to 6 hours, and the curing of the coating film varies depending on the type of silane compound. For example, when a silane medium having an epoxy group is used, it is appropriate to proceed at 120 to 200 ° C. for about 0.5 to 6 hours. When a silane medium having a vinyl group or an acrylic group is used, 150 hours is required. Heat treatment is performed at 230 ° C. for 0.5 to 6 hours, and after heat treatment at 120 to 200 ° C. for 0.5 to 6 hours, it is cured by irradiation with ultraviolet rays for about 3 minutes.

  Referring to FIG. 1, it can be seen that the dielectric film according to the present invention exhibits the best flexibility, and the thickness of the produced film depends on the viscosity of the hybrid material used for coating. In the range of 3 to 10 μm.

FIG. 4 shows the dielectric properties at room temperature of a non-organic barium titanate hybrid film using 3-methacryloyloxypropyltrimethoxysilane as a medium and having a crystalline barium titanate particle content. As a result of measuring the dielectric properties of the barium titanate hybrid material by changing the barium titanate content from 0 to 9.0% by weight, the measured dielectric constant (ε _r ) value of the measured frequency (1 to 100 z) Although it changed little by little, it had a range of 4.9 to 65.3. The dielectric constant of the barium titanate hybrid film according to the present invention tends to increase depending on the content of barium titanate contained. On the other hand, it tends to weaken as the operating frequency increases. The increase in the dielectric constant due to the added barium titanate content is due to the effect of the arithmetic mean and the spacing between the oxide particles due to the increase in the high dielectric constant barium titanate content in the low dielectric constant medium. This is considered to be due to further narrowing and increased dipole-dipole interaction within the hybrid material.

Bhattacrarya and Tummala are PMN (lead magnesium niobate) -PT (lead titanate) / epoxy (epoxy) complex (S. Bhattacharya, RR Tummala, J. Microelectron. 32 (2001) 11) and ε _r is 29. According to Lam et al. (KH Lam, HLW Chan, HS Luo, QR Yin, ZW Yin, CL Choy, Microelectron. Eng. 66 (2003) 79), 65 PMN-35PT powder has high transmittance and ferroelectricity. A hybrid is disclosed in which ε _r is between 45 and 50 dispersed in a copolymer (ε _r ≈10). The largest paper in Kuo et al. (DH Kuo, C. -C. Chang, T. -Y. Su, W. -K. Wang, B. -Y. Lin, Mater. Chem. Phys. 85 (2004) 201) epsilon _r discloses a 44BaTiO ₃ / epoxy (epoxy) complex. The no / organic barium titanate hybrid film according to the present invention is a dielectric, although barium titanate contains 9% by weight (about 2% by volume) in the hybrid film, which is very low compared to the previous study. The constant (ε _r ) value was 65.3, which was extremely high.

  As described above, the non-organic barium titanate hybrid dielectric film according to the present invention has a high dielectric constant because of the compatibility of the non-organic hybrid polymer material used and the uniformity of the barium titanate particles to the polymer material. It is judged to be due to dispersibility.

  Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are merely illustrative of the present invention, and the claims of the present invention are not limited to the following.

<Production Example 1>
(Production of crystalline barium titanate nanoparticles)
Titanium isopropoxide used in the present invention (Ti (OPr ⁱ ) ₄ or TTIP, 97% Aldrich product), barium hydroxide-8 hydrate (98 +%, Aldrich product), ethylenediamine (EDA, 98 +% Daimasa Chemical, Japan) was used as is without additional purification steps. All other chemicals and solvents were reagent grades sold by Sigma-Aldrich and used as purchased without additional purification steps. Deionized water was used after purging dry nitrogen (N ₂ ) to remove CO ₂ .

Ba (OH) ₂ · H ₂ O (1.67 g, Ba / Ti molar ratio = 1.0) is added to 50 g of deionized water from which CO ₂ has been removed, and stirred at 50 ° C under N ₂ to produce an aqueous barium hydroxide solution. To do. Titanium isopropoxide and ethylenediamine (EDA) were added to 10 g of isopropyl alcohol and stirred at 50 ° C. for 30 minutes to prepare a Ti-EDA mixture. At this time, the amount of ethylenediamine added was adjusted in the range of 1 to 10 on the basis of the EDA / Ti molar ratio as shown in Table 1 below. The Ti-EDA mixture was added to the aqueous barium hydroxide solution and stirred at 70 ° C. for 2 hours. All the above reactions were carried out under a nitrogen atmosphere in a polypropylene reactor coated with Teflon.

  The produced crystalline nanoparticles were collected by centrifugation (17000 rpm, 20 minutes), and then the obtained crystalline barium titanate nanoparticles were dispersed in methanol for 30 minutes using ultrasonic waves, and then centrifuged. The separation method was advanced twice to remove moisture on the surface of the barium titanate nanoparticles, and crystalline barium titanate nanoparticles substituted with methanol instead of moisture were produced.

<Production Example 2>
(No / manufacturing of medium for organic barium titanate hybrid materials)
The no / organic barium titanate hybrid media was produced by an improved sol-gel process. After dissolving 5.1 g of 3-methacryloyloxypropyl trimethoxysilane (MPTS) (98%, Aldrich) into 5.1 g of isopropyl alcohol (IPA, Aldrich) at room temperature with stirring. Then, 1.0 g of 0.1 M HNO ₃ solution was added dropwise to the MTPS-IPA solution, and the reaction mixture was stirred at 70 ° C. for 2 hours, and then the pressure was reduced to remove IPA as a reaction byproduct. When toluene and distilled water are added to the reaction product, the reaction mixture is separated into a toluene layer in which the alkylsiloxane reactant is dissolved and an aqueous layer in which hydrogen ions, nitrate ions, etc. remain. After separating only the toluene layer, toluene was removed under reduced pressure at 50 ° C. to obtain a viscous, light and pale yellow purified medium. The medium was dissolved in most organic solvents such as toluene, cyclohexane, methanol, DMF.

<Production Example 3>
(No / manufacturing of medium for organic barium titanate hybrid materials)
The no / organic barium titanate hybrid media was produced by an improved sol-gel process. After dissolving 4.85 g of 3-glycidyloxypropyltrimethoxysilane (GPS) (98%, Aldrich) into 4.85 g of isopropyl alcohol (IPA, Aldrich) with stirring at room temperature, 1.0 g of 0.1 M HNO ₃ solution was added dropwise to the MTPS-IPA solution, and the reaction mixture was stirred at 70 ° C. for 2 hours, and then the pressure was reduced to remove IPA as a reaction byproduct. When toluene and distilled water are added to the reaction product, the reaction mixture is separated into a toluene layer in which the alkylsiloxane reactant is dissolved and an aqueous layer in which hydrogen ions, nitrate ions, etc. remain. After separating only the toluene layer, toluene was removed under reduced pressure at 50 ° C. to obtain a viscous, light and pale yellow purified medium. The medium was dissolved in most organic solvents such as toluene, cyclohexane, methanol, DMF.

<Example 1>
(No / Manufacturing of barium titanate hybrid material)
A non-organic barium titanate hybrid was prepared by combining the crystalline barium titanate prepared from Production Example 1 and the non-organic hybrid medium derived from MTPS produced from Production Example 2.

  First, the crystalline barium titanate produced from Production Example 1 was dispersed in dry methanol by ultrasonic treatment for 1 hour, and the non-organic hybrid medium produced from Production Example 2 was dissolved in the dispersion. At this time, as shown in Table 1 below, the barium titanate content was changed from 0 to 9% by weight based on the total mass of barium titanate and the non / organic hybrid medium. The mixed solution in which the non / organic hybrid medium and barium titanate were mixed was sonicated at room temperature for 30 minutes, and then refluxed at 70 to 80 ° C. for 4 hours.

  Methanol was evaporated at 70 ° C. to have a viscosity compatible with spin coating, and then a polyethylene film was spin coated (2000 rpm, 20 s) to form a no / organic barium titanate hybrid film. After spin coating, it was dried in air at 100 ° C. for 4 hours and then cured at 150 ° C. for 4 hours. The resulting barium titanate hybrid film had a thickness of about 5 to 7 μm.

Characteristic analysis for no / organic barium titanate film is Rigaku D / Max-2200V X-ray diffractometer (CuKα = 1.5418Å) and infrared spectrometer (FT-IR spectrometer) Win from Bio-Rad -IR, FTS-165 was used. An impedance analyzer Agilent 4294A was used to measure the capacitance of the no / organic barium titanate (BaTiO ₃ ) hybrid film. The dielectric constant of the hybrid film is the equation
<Equation 1>
Calculated from Where “r” is the dielectric constant of the hybrid film, “d” is the thickness of the hybrid film, “A” is the area of the electrode, “c” is the measured capacitance, “Ε ₀ ” is a dielectric constant (8.854 × 10 ⁻¹² F / m) in vacuum. The thickness of the hybrid film was measured using an α-step 500 facility from KLA Tencor.

<Table 1>

  FIG. 2 shows an XRD (X-ray diffraction) pattern for the hybrid film produced from Example 1. It was found that the barium titanate nanoparticles produced from Production Example 1 had a 2θ value at the same position as the XRD pattern, and it was found that the crystallinity did not change while the barium titanate nanoparticles were produced with a hybrid film. .

FIG. 3 shows the FT-IR spectrum of the hybrid film manufactured from Example 1, which showed characteristic values of 500 to 4000 cm ⁻¹ . Comparing the measured FT-IR spectrum with the pure MTPS spectrum and barium titanate spectrum as shown in Fig. 3, it can be seen that the position of the peak is slightly shifted. It is a peak of partially hydrated MTPS and barium titanate. For example, 563 cm ^-1 (Ti-O); 1370, 1447 cm ^-1 (Ti-OH); 822, 1170 cm ^-1 (Ti-O-Ti); 1050, 1208, 1283, 1500 cm ^-1 (CN of C-NH) ₂ and NH of NH ₂ ), 1640, 3440 cm ⁻¹ (OH of H ₂ O); 2850, 2935 cm ⁻¹ (CH) commonly appear from two bulk and hybrids. Si-O / Si-OH (980 cm ^-1 ); Si-O-Si (1088, 1170 cm ^-1 ); SiC-H (1296 cm ^-1 ); Si-C (1455 cm ^-1 ) and C = O ( A new peak such as 1727 cm ⁻¹ ) was observed, which is confirmed to be related to MTPS. Two new peaks were observed at 925 cm ⁻¹ and 1375 cm ⁻¹ , which are related to Ti—O—Si. Ti-O-Si network formation is probably due to condensation of OH groups on the surface of barium titanate and partially hydrated MPTS [R-Si (OMe) _3-x (OH) _x ].

<Example 2>
(No / production of organic barium titanate hybrid material)
A crystalline / barium titanate produced from Production Example 1 and a medium derived from GPS produced from Production Example 3 were combined to produce a no / organic barium titanate hybrid.

  First, the crystalline barium titanate produced from Production Example 1 was dispersed in dry methanol by ultrasonic treatment for 1 hour, and the hybrid medium produced from Production Example 3 was dissolved in the dispersion. At this time, the barium titanate was intruded so as to be 25% by weight based on the total mass of the barium titanate and the non / organic hybrid medium produced from Production Example 3. The mixed solution in which the non / organic hybrid medium and barium titanate were mixed was sonicated at room temperature for 30 minutes, and then refluxed at 70 to 80 ° C. for 4 hours.

  After evaporating methanol at 70 ° C. to have a viscosity suitable for spin coating, the polyethylene film was spin coated (2000 rpm, 20 s) to form a no / organic barium titanate hybrid film. After spin coating, it was dried in air at 120 ° C. for 1 hour and then cured at 200 ° C. for 2 hours. The thickness of the manufactured barium titanate hybrid film was about 6.4 μm, and the dielectric constant was 90 .3.

  The present invention is a method for uniformly dispersing high-concentration crystalline barium titanate nanoparticles having excellent dispersibility in an organic solvent using a medium produced by a hydrolysis reaction and a crosslinking reaction of a silane compound. A method for producing a barium hybrid and a high dielectric constant flexible dielectric film using the same are provided.

  The non-organic barium titanate hybrid dielectric film according to the present invention has a high dielectric constant because of the compatibility of the non-organic hybrid medium used and the chemical between the barium titanate particles produced by the specific production method and the medium. This is considered to be due to the transformation to a solid structure that is easy to form with excellent dielectric properties due to bonding. Therefore, the no / organic barium titanate hybrid film prepared according to the present invention has a high dielectric constant even at a relatively low barium titanate content, and thus has an advantage of excellent flexibility and dielectric properties.

2 is a photograph of a no / organic barium titanate hybrid film formed on a plastic substrate. FIG. 5 is an X-ray diffraction pattern for a barium titanate powder produced from Production Example 1 and a non-organic barium titanate hybrid film containing 4.5% by weight of the barium titanate. FIG. It is the result of the infrared spectroscopic analysis with respect to the no / organic barium titanate hybrid film (b) which contained pure MPTS (a) and MPTS hydrolyzate as a medium, and contained barium titanate content 4.5weight%. It is a graph which shows the change of the dielectric constant of the non / organic barium titanate hybrid film by barium titanate content.

Claims (15)

1) A step of adding an acid to one or more silane compound solutions represented by the following chemical formula 1 and heating to produce a medium for no / organic hybrid; and 2) crystalline titanic acid in the medium for no / organic hybrid; A method for producing a no / organic barium titanate hybrid comprising: dispersing barium nanoparticles to produce a no / organic barium titanate hybrid;
<Chemical Formula 1>
(R ¹ ) _n Si (OR ² ) _4-n
Wherein n is an integer of 1 to 3; R ¹ is a vinyl group or an alkyl group having 1 to 10 carbon atoms having a reactive group, and the reactive group is a (meth) acrylate group, a vinyl group or An epoxy group, wherein the alkyl group contains a heteroatom selected from N, O or S; R ² is alkyl or alkenyl having 1 to 5 carbon atoms.) 2. The method for producing a no-organic barium titanate hybrid according to claim 1, wherein the silane compound is selected from the following chemical formulas 2 to 4.
<Chemical formula 2>
<Chemical formula 3>
<Chemical Formula 4>
(In the formulas 2 to 4, R ² is the same as defined in formula 1, R ³ is hydrogen or methyl, A is independently a chemical bond and alkylene having 1 to 10 carbon atoms. The alkylene contains an oxygen atom in the carbon chain.)   The silane compound may be 3-methacryloxypropyltrimethoxysilane (MPTS), 3-glycidyloxypropyltrimethoxysilane (GPS), or vinyl triisopropenoxysilane (MPTS). Vinyltriisopropenoxysilane (VTIPS) is selected, The manufacturing method of the non / organic barium titanate hybrid of Claim 2 characterized by the above-mentioned.   The crystalline barium titanate nanoparticles may be 0.5 to 40% by weight based on the weight of the non-organic hybrid medium and the crystalline barium titanate nanoparticles combined. A process for the preparation of the described no / organic barium titanate hybrid.   The method according to claim 1, wherein the step 1) further comprises removing an acid used as a hydrolysis catalyst by a solvent extraction method, and distilling the solvent under reduced pressure to obtain a medium for non-organic hybrid. Method for producing no / organic barium titanate hybrid.   The non / organic titanic acid according to claim 1, further comprising the step of coating the non / organic barium titanate hybrid on the substrate after the step 2), and drying and curing to form a film. Production method of barium hybrid.   The method for producing a no / organic barium titanate hybrid according to claim 1, wherein the acid is nitric acid. Crystalline barium titanate nanoparticles are
(A) a step of dissolving a titanium alkoxide and a diamine compound of the following chemical formula 5 in a solvent to produce a mixed solution;
(B) The mixture is added to the barium hydroxide aqueous solution and then stirred to form barium titanate; and (c) produced by a production method comprising the step of separating the barium titanate. The method for producing a no / organic barium titanate hybrid according to any one of claims 1 to 7.
<Chemical formula 5>
(In the formula, R is selected from alkylene groups having 2 to 8 carbon atoms.)   The method for producing an organic / barium titanate-free hybrid according to claim 8, wherein the molar ratio of the diamine compound to the titanium alkoxide is 1 to 20.   The method for producing a no / organic barium titanate hybrid according to claim 9, wherein the molar ratio of the diamine compound to the titanium alkoxide is 3 to 10.   The method for producing an organic / barium titanate-free hybrid according to claim 8, wherein the diamine compound is ethylenediamine (EDA) or propanediamine.   A no / organic barium titanate hybrid produced by the production method according to claim 1.   A barium / organic barium titanate hybrid produced by the production method according to claim 8.   A flexible dielectric film having a high dielectric constant, which is manufactured by coating the substrate with the organic / barium titanate hybrid according to claim 12 and then drying and curing the hybrid.   A flexible dielectric film having a high dielectric constant, which is manufactured by coating the substrate with the barium / organic barium titanate hybrid according to claim 13 and then drying and curing the hybrid.