TW201238758A - Soluble polyimide/silica-titania core-shell nanoparticle hybrid thin film and its preparation - Google Patents

Abstract

The present invention relates to a soluble polyimide/silica-titania core-shell nanoparticle hybrid thin film and the method for preparing the same. The method comprises coating colloidal silica with titania precursor under Stober condition and then hydrolyzing to obtain a silica-titania core-shell nanoparticle, then dehydrating and esterifying the silica-titania core-shell nanoparticle with polyimide having carboxyl group via spin-coating process to obtain a polyimide/silica-titania hybrid film.

Description

201238758 VI. Description of the Invention: [Technology of the Invention] Field of the Invention The present invention relates to a mixed film of a soluble, pure imine, luxury rice microparticle and a method for producing the same. /, Titanium Oxide [Previous Technology] ° Organic-inorganic hybrid materials are difficult to process due to their superiority to the 撼 撼 ΐ dielectric material being converted into a high-temperature polymer and thus exhibit poor processability. The fluorocarbon monomer (for example, 4,4, (hexafluoropropylene) diphenyl y good mechanical properties ij engraved with two = imine and inorganic filler-based mixed materials will solve the problem of adhesion of the benefits of mixed materials Has been extensively studied. Polymethane Imine Plant..., Hirose 3 Oxide Oxide, Layered Oxide Oxime such as Montmorillonite Decoction 1te)) or Mica, Aluminum Nitride, Titanium Oxide, Barium Titanate and Carbon Nano Report. The prepared hybrid material shows that significant hot money, mechanical strength and physical properties can be achieved when incorporated into a suitable no-filler. The poly-imine-oxidized stone and the poly-imine-titanium oxide are mixed in various materials, including the electronic device, the material of the optical waveguide, the material of the Si Nan, the material with high transparency, and the non- Linear optics / raw materials, electrical, (bw-k) materials, photovoltaic devices and fuel cells. Usually, polyphosphonium oxide or poly-imine and oxidized mixed materials can be used respectively to make polyoxygenated neonatal chest, such as tetraethoxy Wei sister oxidized capsule according to sol gel (10) Process preparation. _, polyimine and oxidized stone or oxygen 201238758 Titanium compatibility is not expected. For this reason, most of the reported hybrid materials rapidly become hazy as the inorganic content increases. This phenomenon is partly due to the rapid expansion of the particle size as the particles in the mixed material prepared by the lysing process are increased. Improving the compatibility between the two phases and the reduction in the size of the inorganic particles can be achieved by preparing a mixed material using a coupling agent. Cerium oxide and titanium oxide precursors have been successfully used to prepare hybrid materials with high optical transparency, coordination, and refractive index; however, the reported particle size of the hybrid material is precisely controlled by the method, and the particle size is applied to the optical application. Very important. Furthermore, the additional coupling agent remaining in the ruthenium blending material may affect important thermal/mechanical/optical properties; - Possible remedy for the money to avoid the addition of titanium to the 'golden oxides without adding extra' Words: Inorganic network structure of oxidized stone or titanium oxide. And ^ίϊίΐί can form core and shell materials from two or more different materials. Compared to a single nanoparticle, the core shell has a iiiif material that can easily control a variety of physical and chemical properties, including = 匕: optical properties. Pre-reflection occurs when P has a different refractive index. Anti-reflective (AR) coatings have been widely used in computer screens, displays and other applications where suppression is required. The lyophilized coating has a number of excellent coating properties in a large area; the material has a good coating property; 5 days ra ύ reduced cost, good optical performance, room temperature (four) followed by _ layer system [invention content] and the following collection (Π) Oxygenamine single = (I_ indicated __) and 201238758 ratio of poly nitrite: oxidation; ^ _ _ titanium oxide core shell nanoparticle in the range: 9〇 to 9〇:

(I) _ In the above, R represents a carboxyl group (-COOH), and Ar, Ar, and Ar" may be the same or different and each represents a phenyl group, a naphthyl group, and a stretching group, wherein X represents a Halogen-substituted Cl_4 alkyl, phenyl_〇, _〇_, _C〇_, _s-, -so- or -S〇2_yl)' m represents a value of i to 30, preferably 2 to 1 The value of 〇

^ According to this batch of miscellaneous, "A bribes and oxygen oxides are too thin to become a film, by changing the rate of oxygen cut oxygen. The refractive index can even be as high as L753, which is utilized in the yttrium and oxygen-cut titanium oxide core shell, which is included in the Stober condition, and the invention relates to a method for producing a mixed film of soluble nano-particles 201238758 After coating the colloidal cerium oxide to obtain the cerium oxide-titanium oxide precursor core-shell nanoparticle, the titanium oxide precursor is hydrolyzed to form cerium oxide-titanium oxide nanoparticle, and then the hydroxyl group on the titanium oxide is used. The poly(imine) having a carboxylic acid group is subjected to a dehydration esterification reaction by a spin coating method to obtain a mixed film of polyimine or oxidized cerium-titanium oxide core-shell nanoparticles. Specifically, the method for producing a mixed film of the soluble polyimine and the cerium oxide-titanium oxide core-shell nanoparticle of the present invention comprises the following steps: (4) coating the oxidation with an alkoxylation under acidic tilting to obtain a ton of cut The ruthenium oxide-alkoxide titanium oxide core-shell nanoparticle granulated with the oxidized oxidized nucleus, followed by hydrolysis to obtain the oxidized dream-oxygen-enhanced naphthalene; (9) the hetero-imine disc with the nucleus The oxygen cut titanium gamma nanometer is reduced by coating and heating on the substrate, and heating the base of the base ΐ 奈 奈 所 进行 进行 进行A compound film of yttrium and oxymium's titanium oxide core-shell nano-particles. In the above step (4), 'oxidation of oxidized oxidized oxime 1 1Ϊ1 after hydrolysis, oxidized stone sulphate and titanium oxide by weight ratio In the case of 1:8 to the top of the 。 。 。 。 。 。 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛Base) is better to dissolve first, but A total & alcohol from the sputum used to treat the desired titanium alkoxide The titanium oxide is produced during the reaction to produce the alcohol in the step (b) and in the case of the titanium oxide of the ship, the solvent is based on the butanol. The weight of the heavy imine of the particle and the refractive index of the final use of the oxide oxide The range of 0:90 is widely changed, and the end-view is most effective: the carboxylic acid-based polyimide anhydride is added to the phthalic anhydride, and the ratio of the dianhydride molar equivalent/second 201238758 is greater than 1. After the acid anhydride ring-opening condensation reaction is carried out to obtain the poly-decanoic acid of the terminal acid anhydride group, the polyamic acid having a carboxylic acid group at the terminal is obtained by reacting an acid anhydride group with a carboxylic acid-containing aromatic amine, followed by sulfimine. That is, a polyimine having a carboxylic acid group is obtained. These processes are known to those skilled in the art, for example, can be obtained by the following manufacturing process: w Reaction Figure 1

In the above, 'R represents a carboxyl group (-COOH) 'Ar, Ar, and Ar" may be the same or different and each represents a phenyl, anthracene, a phenyl group, a _ph_x_ph_ group (wherein X represents a halogen-substituted group) CM alkyl group, -〇-phenyl_〇, _〇_, _c〇_, -S-, -SO- or _s〇2_ group), m represents a value of 1 to 30, preferably 2 The value of Zhichuan 201238758; and x/y>l. Examples of the aromatic dianhydride which produces the polyamidiamine having a carboxylic acid group in the present invention may, for example, but not limited to, 4,4,-(hexafluoroisophthalene) Propyl)di-p-phthalic anhydride (6FDA), pyromellitic dianhydride, 4,4,-oxydiphthalic anhydride, 3,3,4,4,_biphenyltetracarboxylic dianhydride, 3 , 3',4,4,-dibenzophenone tetracarboxylic dianhydride, ethyltetracarboxylic dianhydride, butadiene tetracarboxylic acid dianhydride, cyclopentanic acid dianhydride, pyromellitic acid Dihydride, 2,2',3,3'-dibenzophenone tetracarboxylic dianhydride, 2,2,3,3,_biphenyltetracarboxylic dianhydride, 2,2_bis (3,4- Dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4_two Carboxyphenyl)sulfone dianhydride, U-bis(2,3-dicarboxyl) Ethylphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)decane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 4,4,_(p-benzene) Oxy)diruthenic dianhydride, 4:4'·(m-phenyldioxy)dicarboxylic acid needle, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 2 4,5,8- Naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, iota, 2,3,4-benzenetetracarboxylic phthalic anhydride, 3,4,9,1 fluorene-diphthalene Two needles of benzoic acid, two needles of 2,3,6,7-indenic acid, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, etc. The aromatic dianhydrides may be used alone or in combination. A mixture of various kinds is used. In the present invention, an example of the aromatic diamine having a phthalic acid group-containing polyimine is exemplified by, but not limited to, 4,4,-(hexafluoroisopropylidene)diphenylamine (6FpDA). ), p-Benzene^, 4,4'-oxydiphenylamine, bis(4-aminophenoxy)benzene, bis(=ethoxy)benzene, 2,2-bis[4- (4-Aminophenoxy)phenyl]propane, bis[4_(4_, phenoxy)phenyl; μ wind, 1,3-bis(3·aminophenoxy)benzene, 4,4 ,: bis(4-aminophenoxy) 3,3'-dihydroxybiphenyl, bis[4_(3-aminophenoxy)phenyl]methane, u_bis[4_nonylaminophenoxy Phenyl ] Ethylene, bis(tetra) 3 ·aminophenoxy) phenylethyl ketone j, 2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2,-bis[4-( 3-aminophenyl)phenyl]butane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3_hexa-propan 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]one, bis[4-(3-aminophenoxy)phenyl] Thioether, bis[4-(3-aminophenoxy)phenyl], bis[4-(3.aminophenoxy)phenyl] hard, bis[4_(3-aminophenoxy) Phenyl ether and the like. The above diamines may be used singly or in combination of plural kinds. The carboxylic acid-containing aromatic amine which produces the polyamidimine having a carboxylic acid group in the present invention 201238758 may be, for example, 4-aminobenzoic acid. The acidity of the amine has the kinetics of the nucleus. In the case of the production of the granules, there is no effect on the reaction, and the temperature is at a temperature of 90 ° C, preferably 30 to 30. Perform the temperature within 75 °C. The solvent used is generally an aprotic polar solvent, the type of which is specific to the plant as long as it does not react with the reactants and products. Specific examples can be ^, Ν-monomethyl acetamide 1jy ^), Ν 曱 曱 咖 各 = =, = ri7M_ (DMF), tetrahydro ° (four) (pass), two Wei, gas imitation ^ \Τί , - methane and so on. Among them, N-methylpyrrolidone (NMP) and 2-methylacetamide (DMAc) are preferably used. These solvents may be used in one or more. Subsequent hydrazine imidization reaction can also be carried out under the reaction temperature, preferably at a temperature of 12 (Fu-150-180 C). The solvent used can be prepared by using the above-mentioned preparation. The solvent used in the step may be the same or different in the respective steps, but in terms of handling convenience, the same solvent system is preferably used. In the method of the present invention, the polyimide obtained by coating the substrate is oxidized. The film forming method of the mixed film of the Shixi-titanium oxide core-shell nano-particles can be carried out by a coating method known in the art, and includes, for example, rolling coating, flow coating (coating), and impregnation coating method ( Dip coating 〆, spray coating, spin coating, curtain coating, etc., in which the spin coating is preferably used from the viewpoint of obtaining a uniform film In the method of the present invention, a method for dehydrating and esterifying a carboxylic acid group contained on a polyfluorene imine and a hydroxyl group carried on a cerium oxide-titanium oxide core-shell nanoparticle is used to cure the coating film by heating , which is generally used for preparing baking of mixed material film It is advisable to use a multi-stage heating bake method. The multi-stage heating bake can slowly evaporate the solvent contained therein to avoid film cracking. The multi-stage baking method used includes, but is not limited to, for example, at 50. -7 (TC baking for 15-25 minutes, then baking at 140-160 ° C for 15-25 minutes, then moving into a high temperature furnace and curing at 290-310 ° C for several hours under nitrogen, finally at 390 It is cured at a temperature of -420 ° C for several hours. 201238758 , for example, the titanium oxide precursor is tetrabutyl titanate, and the polyimide is made of 4"4 tian isopropyl isopropyl) diphenylamine (6FpDA), 4, 4 Hexafluoroisopropylidene)diphenyl'=2^_=_acid (4 repeated 靡_, indicating the reaction of the present invention. Figure 1. Flow chart for preparing oxidized titanium oxide core-shell nanoparticles

乂)HH〇-((Si〇2)V〇H ten condensation

+ H2〇 HCI

BuO BuO BuO

BU0N^BU0 at.n BuO Ti BuO^ Λ BUO^I, I bBU° T,. 0 ^Ti—BuO

〆〇 &U〇 Ti BuO〆· ' Λ BuO _ BuO 0 I

BuO

0-~^S 丨 02)^_〇—Bu〇 BuO. 8u0 BuO’ 'BuO

8uO-H 201238758 Reaction Scheme 2. Preparation of Polyimide/Iron Oxide_Titanium Oxide Nanoparticles Mixed Film

6FDA

6FpDA ^T1 in sputum for 8 hours at room temperature

Polylysine 2HQ 丄 16 hours at room temperature W.

Hot-bulk imidization: 0 CFj is in the "night oil at 18 〇. 〇 8 hours

Spin coating, heating '6 ° ° C, 20 minutes 100 ° C, 20 minutes 150 ° C, 20 minutes 300 ° C, 卯 minutes (under vacuum), in DM ^ c: at room temperature 1 stirring 2 Hour -h2o ' ? τί1

Ο-η*·〇·

〇—Ti-o-{(Sl〇j). 0

The present invention will be specifically described by the following examples, which are intended to be illustrative only and not to limit the scope of the invention. The examples used materials 4,4'-(hexafluoroisopropylidene)diphenyl phthalic anhydride (6FDA, 99 〇 / 〇) and 4, 4, - (six 201238758 isopropylidene) diphenylamine (6FpDA, 99%) was obtained from Chriskev (Lenea, USA). 4-Aminobenzoic acid (4ABA, 99%), aniline (99.5%) and tetrahydrofuran (THF, 99.9%) were obtained from ACROS (Geel, Belgium). Sterols (MeOH, 98%) were obtained from Mallincrodt. All monomers were purchased and used directly without purification. 1-Mercapto-2-pyrrolidone (NMP, 99.9%), 1,3-dichlorobenzene (DCB, 99.9%) and N,N'-dimercaptoacetamide (dmac, 99.5%) were obtained from TEDIA (Fairfield, USA). Barium butoxide (Ti(〇Bu) 4, 99%) was obtained from ACROS (Ged, Belgium). Colloidal cerium oxide (Nissan Chemical Industries, Inc., 12-15 nm, 30% by weight in isopropyl alcohol) and Silecs RXC530 (Silecs) were used to obtain the state. Example 1 - Synthesis of Soluble Polyimine with Terminal Carboxylic Acid Group (6FDA_ 6FpDA-COOH) Synthesis of Organic Soluble Polyimine with Terminal Carboxyl Group Using Solution Iridium Amine Technology (6FDA-6FpDA- COOH). The molecular weight and terminal functional groups are controlled by the stoichiometry of the reactants. First, 2.01 g (0.006 mol) of 4,4,-(hexafluoroisopropylidene)diphenylamine (6FpDA) was added to a 1 ml three-necked round bottom flask and the reaction was dissolved using 29.1 ml of NMP. . Next, 5.331 g (0.012 mol) of 4,4'-(hexa-isopropylidene)diphthalic anhydride (6FDA) was slowly added under nitrogen purge to the above solution and stirred vigorously. The mixture was allowed to react at room temperature for 8 hours. Next, 1.6457 g (0.012 mol) of 4-aminobenzoic acid (4ABA) and 7.2 ml of 1,3-dichlorobenzene were added to the above solution. After stirring the reaction for 16 hours at room temperature, 20 wt% poly(proline) (PAA) was formed. The PAA solution was then re-imidized in 180 C of oil > trough for 8 hours and cooled to room temperature. The homogenized 6FDA-6FpDA-4ABA-COOH solution was immersed in 500 ml of sterol and re-dissolved in 30 ml twice. The off-white precipitate was recovered and taken at 15 Torr. After drying in a vacuum for 24 hours, 2.136 g of 6FDA-6FpDA-4ABA-C00H (yield: 23.8%) was obtained. The average acid value of 6FDA-6FpDA-4ABA-C00H was determined by titration to be 14 mg KOH/0.5 g of polyimine. The average molecular weight estimated from this acid value is about 4,000. The weight average molecular weight estimated by GPC was 4,276 and the polyunion was 1.31. It was found that 6FDA, 6FpDA and 4ABA were respectively 244-247 ° C, 195-198 ° C ^ _ 12 201238758 187-189 ° (purification, 6 卩〇8) by sublimation/condensation step before polyimine synthesis. -6卩1)〇八-4八三入-(: The yield of 0011 can be changed to about 50%. ^ Prepare 6FDA-6FpDA_4ABA-CO〇H film using the following procedure: 0.5 g 6FDA-6FpDA-4ABA -COOH was dissolved in 5 ml of DMAc' while stirring. After filtering with a 45.45μιη PTFE filter, it was spin-coated on Shishi wafers at 1000 rpm for 20 seconds. Then the film was baked on a 60 ° hot plate for 1 minute. And baking at 150 jC for 30 minutes to evaporate the solvent. This 6FDA-6FpDA-4ABA-COOH cured film was referred to as PST0 in comparison with the polyimine-titanium oxide mixed film (PST10-PST90). The characteristic peaks of the FTIR spectrum are as follows: 3434cm-1 (COOH), 1788(^((^0), 1726(^(^0), 1610(^(03⁄4), 1517^^(3⁄43⁄4), 143801^(3⁄43⁄4) , 1370cm-1 (CN) 〇 Example 2 - Polyimine / SiCVTiO2 core-shell nanoparticle mixed film synthesis The composition used to prepare the film is listed in Table 1 below, and is called ρ8τχ (χ indicates Mixed film The theoretical amount of addition of cerium oxide-titanium oxide nanoparticles is as follows. Using PST5 〇 as an example, firstly, the gram (2 5 χ 1 〇 - 2 m) Ti (〇Bu) 4, 0.625 g (1.04 X 10 · 2 Mol) colloidal cerium oxide and 1 ml of butanol were added to a 2 ml round bottom flask and stirred for 30 minutes. Then, 0.45 g of deionized water and 0.1 g of hydrochloric acid (HC1 37 wt%) were added dropwise to the above solution. 2 hours. 0.2 g of 2.5 liters of DMAc (1 736 >< 10-4 Mo, 6FDA-6FpDA-COOH) was added dropwise to the above mixture with a syringe. The mixture was then allowed to mix at room temperature. 〇分^ Obtain the PST50 precursor solution. The precursor solution was filtered through a crucible 45 and sprayed on a crucible wafer at 2000 rpm for 2 sec. The resulting PI/SiOrTi〇2 mixed film (PST1 〇_PST5〇) It is further treated by immersion in boiling water in a hydrothermal process and refluxed for 12 hours. After the above process, the film is dried on a 1 〇 hot plate to remove residual water. Various techniques such as ftir, tga, DSC, SEM, TEM, AFM, UV_Vis, and n&k inspection of polyimine/SiO 2 -Ti02 core-shell hybrid materials. 13 201238758 No. 6FDA 6FpDA 4-ABA Complex ( Si〇,-TiCM PST0 40 20 40 0 tsj Λ5. 3 W ^Wl/0^ PST10 36 18 36 10 ' X 15 PST20 32 16 32 20 15 PST30 28 "14 28 30 15 PST40 24 12 "24 40 15 PST50 20 10 20 50 15 Example 3 - Preparation of a three-layer antireflection film The experimental procedure for preparing a two-layer antireflection film is described below. The obtained polyimine/cerium oxide-titanium oxide precursor solution pST50 (first layer) was spin-coated on the FEA glass substrate at a speed of 4 rpm for 30 seconds. The coated film was then cured on a 60 ° C hot plate for 20 minutes at 〇 (TC curing for 2 〇 minutes, at 15 (rc curing for 20 minutes and at 30 (TC curing for 60 minutes. The first layer temperature was cooled to the chamber). After the temperature, the polyimine/titanium oxide precursor PST9(R) (second layer) was spin-coated on the first layer at 7 rpm for 30 seconds. The coated film was then placed on a 6 〇〇c hot plate. Curing

Curing for 20 minutes at 100 Torr, 20 minutes at i5 °C and 60 minutes at 3 °C for 20 minutes. After the second layer temperature was cooled to room temperature, the F_oxime solution (second layer) was spin-coated on the second layer at a speed of 3500 rpm for a second. The coated film was then cured on a 200 ° C hot plate for 5 minutes. The process was the same as the preparation of the antireflective film on the substrate, but the curing temperature on the hot plate was 6 Torr.加热 Heat for 20 minutes and heat at l ° °c for 2 hours. A three-layer antireflection film was obtained. Characterization: 'The Fourier Infrared (FTIR) spectrum of the resulting film was obtained on a double polished twin circle using a Perkin Elmer Spectrum One spectrometer. Gel permeation chromatography (GPC) analysis was performed on a Lab Alliance RI2000 instrument (a column, MIXED-D, available from Polymer Laboratories) connected to a refractive index detector (available from Schambeck SFD GmbH). All GPC analyses were carried out using a polymer-N,N-dimethylformamide (DMF) solution at a flow rate of 1 mL/mim at 70 ° C and corrected for polystyrene standards. The particle size distribution was measured using a particle size meter (Malvern instrument). This uses the backscattered light of the 633 nm He/Ne laser diode 14 201238758 to measure the Brownian motion of the particles to _state light scattering (DLS). The non-negative least squares LS used by the Malve body is used to calculate the equivalent spherical particle size distribution from the measured auto-corrected data. Thermal specific gravity (TGA) and differential scanning calorimetry (DSC) were performed using a TA instrument Q50 and Q20 DSC/RCS9〇 system under continuous nitrogen flow at a heating rate of 2〇t:/min and 10°C/min. The particle size of the inorganic material and the microstructure of the prepared film were examined using a high-resolution transmission electron microscope (HRTEM, JEOL, JEM-2100). Using X-ray diffraction on an X-ray diffractometer (XRD, PANalyticd, X, pert pro MpD) using CuKa radiation (1.5406 angstroms) at a temperature equivalent to the intensity of the focused beam from the rotating anode generator at room temperature Shoot. The fracture surface of the hybrid film was examined by a 曰=H-2400 scanning electron microscope (SEM). The surface morphology of the coated film was examined using an atomic force microscope (Veec® DI3100 AFM). The transmittance of the film coated on the quartz substrate was measured using a Jasc® v_65® UV/Vis/NIR spectrometer. The refractive index (η) and the extinction coefficient (k) of the prepared film in the range of 19 Å to 9 Å were measured using an ellipsometer (GES-5E SOPRA). The thickness (h) of the prepared film was also measured. Table 2 lists the properties of the prepared polyimine/titanium oxide material pST〇_pST1〇〇 = . The three-layer antireflection film was theoretically studied using an optical film design software (Thin Film View, T0H0 TSUSH〇 INC.) to obtain optimum film reflectivity and thus to obtain an optimum layer thickness and refractive index. Table 3 lists the properties of the three-layer antireflection film prepared on the FEA glass and PMMA (poly(methacrylate) substrate, respectively. Results and discussion 1. Polyetherimine-titanium oxide mixed film properties The formation of poly(proline), polyimine and pj/Si〇2_Ti〇2 mixed materials was confirmed by FTIR analysis. Figure 1 illustrates the FTIR spectra of ρι and PI/Si〇2-Ti〇2 films on a double-polished germanium wafer. From Figure 1, it can be observed that the amine (iv) and hydroxyl (OH) 3400-3100 (^1 absorption ' and the absorption of the indole carbonyl at 1680 cm-1. Poly (proline) heated to convert to polyimine Poly(proline) ruthenium imine to chiral amine ring system disappears by 1680 cm-1 in the spectrum and 1785 cm-1 (C=0 asy, str.), 1725 cm-1 (C=Oasy, str.) and 1368cm-丨(C-Nstr) 醯 15 15 201238758 The amine-based absorption peak appeared and was confirmed. The above peaks are the absorption of the quinone imine group, and the spectrum of the thin film of PI/Si〇2_Ti〇2 is mixed. Machine = strong broad absorption observed in the range of 400-850 cm· (corresponding to Ti-〇_Ti network) and 92〇_1100 cm· (equivalent to Si-0-Ti and Si-0-Si, network) $ can be enhanced by increasing the content of Si〇2_Ti〇2 core-shell nanoparticles. ^ 2. Morphological analysis is bare, 2 indicates the viscosity and shear of the PST0_PST50 and Si〇rTi〇2 core-shell solutions. The change in rate. The results show that the shear rate of the shearing force of the sample is roughly increased _ and thus the prepared polyimine and polystyrene/SiCVTi〇2 solution behaves like a brown plastic fluid. psT polyimine / SiOrTi〇2 (PS The viscosity of the solution of T10-PST50 and PST100) calculated from the ratio of shearing shore force and shear rate is 2_4 centipoise. The viscosity is almost fixed. Si (the effect of VTi〇2 content on viscosity is not obvious,

The t-reported naomi records are self-dispersive. The crystals of the oxidized shells were detected by Raman spectroscopy. Figure 3 illustrates the H and pi/Si〇2_T spectra. The figure also shows that the pure Si〇2_Ti〇2 core-shell nano-micro is the first to be compared. As shown in Fig. 3, it was observed that the sharp peaks of the sharp crystals were observed, 515 = and 640 (the characteristic peaks of ^. No other characteristic peaks of the crystal phase f f Qin mine were observed). These results show that the M phase is purely reduced ore after the hydrothermal process of the crystalline titanium oxide. In addition, the intensity of the sharp bribery belt increases with the percentage of the wide-grain particles. These results show that Si〇2_Ti〇2 nanoparticles have successfully penetrated into the polyimide matrix. 4 shows a pattern of powder prepared from polyimide (PST〇), polyimine/Si〇2_Ti〇2, and pure (PST1〇〇) film. As far as PST0 is concerned, it is 20=10~20. A very wide peak was observed in the range. This broad peak is assumed to be due to the amorphous phase of poly. When the content of oxidized ♦•TiO2 in the mixed material increases, the intensity of the oxidized crystallization peak in the range of ^ 2Θ 23~28 gradually increases. At psT, it is a step-enhanced titanium oxide crystal with 7 distinct crystalline peaks Ρ 25.23, 37.13. 37.82. 38.51. 48.06. , 53.98. And 55.05. Corresponding to anatase titanium oxide phase (1〇1), (1〇3), (〇〇4), (ιΐ2), 16 201238758, respectively, is about 18 nm. The peak of the 瘩 庠 庠 丄 丄 八 八 八 八 八 j j j j j j X X X X X X X X X X X X X X X X X X X X X X X The Debye_Sche program is as follows: d

kX βο, ο^θ crystal ^ is the peak position (not 0 0). Figure 5 shows that it is not painted in the stone circle. The Si〇2_Ti〇2 core-shell nanoparticle film

〇.35·lattice stripe and 4 nanometer crystals of diameter are all scattered in the whole; solid J lattice spacing. The results obtained by the measurement and analysis instructions; = 101) The diffraction pattern also shows that the crystal is crystallized with anatase ,2, and the second is J. The size of the inorganic region estimated by the image is 18 2 = (b) Explain that Guangzheng is aware of the loss. In addition, it was found that the titania shell was on the oxygen cut nm: as shown in Fig. 5-5(e). It should be noted that no anatase nanocrystals were observed in the core-shell nanoparticles without a hydrothermal process. These results show that the J m crystals are formed on the film by hydrothermal treatment. Figure 6 “Composition of colloid & 〇2 and Si〇2_Ti〇=軏冰=integral rate particle size distribution obtained by dynamic light scattering (DLS) method of persimmon. This figure shows that this result of 92 4% core-shell particles corresponds to The self-contained, coffee M and the well-derived ί 1 Μ, FESEM and XRD analysis, the prepared oxidized stone oxime-oxidized nucleus granules _ is 18_2Gnm. She is the most common body oxygen enthalpy 2_ΐ5 = ς average particle size, can be estimated The thickness of the oxidized gambling is about 2_4·. This is in accordance with the oxygen-carrying shell obtained from the wealth image 2.5nm. Theoretically, the oxygen-cutting-oxygen, the irradiance increases with the increase of the thickness of the TiO2 shell, because the H/SievnO2 is mixed. The optical properties of the film and thus the anti-reverse & 17 201238758 ί 曰irti invention, the thickness of the titanium oxide shell in different film compositions is the most important factor in the optical properties of the film.

Siof τίο, the ratio. ® 7 shows FE-SEM micrographs of the prepared polyimine / 4 film, (4) PST100 and age mixed with the yin _ _ red health distribution is equivalent to iL tt f condensed. Even in the case of the PST 100, the granules: the second preferred material can be regarded as a homogeneous nanocomposite, which can be used as a method. The date of this issue, the amount of _ and hci and its addition. Because of the == preparation of the nuclear structure - the importance of taking nano particles. In the dilute acidic medium in which /σ H2〇 and HC1 are added, the ratio of the concentration of si〇H and 斗夕之之 to the T_U)4 ′′ δ of the titanium oxide particles is more remarkable. The reaction time is another factor that controls the particle size and particle size distribution of the core shell. Generally, if the reaction time exceeds 2 hours, the particle size and its distribution will be shown; 8 is a simple diagram of PST3〇 and pST5〇 mixed into a thin 臈. This illustrates how the 1 nucleocapsid nanoparticle is evenly distributed in the mixed film. Others derived from 酉' imine film (PST0) and mixed film (pST1〇_pST5〇) are listed in Table 2 below. The average roughness (9) and the average flat root roughness (6) of the PST0-PST100 film were in the range of 0 418_7 378 and 527 527_9 157 coffee, respectively. The table shows that Ra & \ with Si (VTi〇2 core shell nanoparticle content 捭 increased. Under each _ condition, the ratio of Weng coarse and thickness is still 1.92 /. Below. The results show that the prepared mixture is thin臈 flatness is good, and

The surface roughness of the stone can reduce damage to the waveguide device. These results further confirmed the feasibility of coating the mixed material of the present invention into a film. And SEM tips for the 醯 醯 与 耻 耻 耻 耻 _ _ _ 赌 赌 赌 赌 赌 赌 赌 赌 赌 赌 赌 赌 赌 赌 赌 赌 赌18 201238758 Table 2 - Properties of PST0 and PST10-PST50 blends prepared

PSTO h(nm)* 'Rt (nm)b ^h-1 (*) /3⁄4 (nm)b R^h-1 (X)ACcy 7*d vcf (N2) rd(*C)d(air) Rwsoo* (wt%XN2) RWj〇〇e ^Cutoff^ (nm) 413 0.418 0100 0 527 013 263 497 496 PST10 psno 3S6 1453 0408 1845 0513 507 480 Π633* Vdh 357 265 1575 26.92 11 5 252 1560 27.53 272 1.113 0409 1442 0530 352 S09 466 52 22 7 254 1581 25.73 PST30 PST40 PST50 238 2Π7 0 889 2 729 1146 354 512 459 2330 1617

2001 364 517 454 65 42 5 249 1 654 24.65 162 2 849 1758 3 568 2203 370 521 451 a. The thickness of the prepared film cb· S depends on the average coarse and the average square root sag [· ί 5% weight loss Temperature f. interception wavelength g. refractive index at 633mn and its nC, ndAnF are at C (656nm), d (589_ 3. thermal analysis Figure 9 illustrates 6FDA-6FpDA-COOH (PSTO) and polyimine / 别〇2_ 〇2 J material PSTIO-PSTSO at a heating rate of 10 / min, the TGA slash in the nitrogen test. All materials studied at a higher than the decomposition temperature of the handle (5% weight The loss) shows good thermal stability. The psT〇 and m3ST5 in Table 2. The thermal decomposition temperature (Td) of the mixed material is A 537. and • The residue at 800C follows si〇2-Ti〇 The amount of j increases and increases = in the mixed material shot has become Wei and people mixed. Higher than 2 in the job test, the residue (compared to the theoretical value) may be due to the cone of the polymer group /, _f after the TGA The black moiety of the polymer precursor is captured in the inorganic matrix. As shown in Table 2, only p is not observed in the PSTlo_psT50 of all the hybrid materials of the 2 machine tools. The inorganic group has immobilized the polymer segment and it has been confirmed by the available data that the addition of the oxidized oxide-titanium oxide nanoparticle is added with g. This heat shows that the prepared film has excellent heat resistance, and 250 173S 2334 19 201238758 Phase separation did not occur between polyimine and cerium oxide-titanium oxide core-shell nanoparticles. 4. Optical properties Figure 10 illustrates the UV-visible spectrum transmittance of PST0 and PST10-PST100 hybrid films. The intercepting wavelength of the mixed film is attributed to the chromophore of the polyimine. The corresponding zone end is red-shifted due to the cerium oxide-titanium oxide content, as shown in Table 2. This zone shift is usually found in sizes less than 20 ΠΠ. Si〇2_Ti〇2 core-shell nanoparticle. This shows that a highly uniform polyimine-nanocrystalline titanium oxide hybrid material has been obtained and all of the hybrid films exhibit low intercept wavelength and high optical transparency. The color of the polyamidimide mixture of the large electron-donating group CF3 in the diamine group can be interpreted as a decrease in the CTC formation of the polymer chain due to its high steric hindrance and lower induced effect. QP3 Base-to-film transparency The effect is the weakened intermolecular dispersion force due to the low polarization of the CF bond. This shows that there is a rice ruler in the prepared polyamidimide-titanium oxide mixed material. Fig. 11 illustrates PSTO, PST1〇 〇 and PST series of mixed film in explosion 8 〇〇: wavelength change in refractive index and green coefficient. The width of the sheet is shown as a function of the oxymium-titanium oxide content. As shown in Fig. U, it increases linearly in the content of titanium oxide, such as the content of titanium oxide, suggesting that the hydrolysis precursor ϋf ΐ 职 职 职Ti, turn, resulting in the refractive index of the job. The soluble imide of arsenic can be successfully obtained, 560^3X20^ li58;, pST3 T^ f ^ m collapse, pr〇 is (7) 5, and psTMg is . PST90 0 ^ makes its optical usability. At 300 d's turtle hair defect 'it will be limited to zero', the prepared mixed film 20 201238758 is transparent. Therefore, it is obvious to avoid the calculation of (7): , , . The value of the Abbe number (Vd) can be obtained by mixing the enamel film of the following formula into a ruthenium film with good optical dispersion. (5), mixed with the preparation of the composite 5. Multi-layer anti-reflective coating, the mixed film has a potential coating in the optical device. Fig. 12 (8) and (b) show the gravitational spectrum of the FEA glass and the two-layer antireflective film of the present invention. The shot shows an anti-spray coating structure. Table 3 below lists the prepared three-layer anti-reflective thin $, _ and 性 上 ΡΜΜΑ ΡΜΜΑ ΡΜΜΑ ΡΜΜΑ ΡΜΜΑ ΡΜΜΑ ΡΜΜΑ : : : : 工 工 工 工 工 工 工 工 η η η η η η η η η η η η η η η η η η η The range is about the anti-God of W, and ΡΜΜΑ (η=1.57 has an average reflection of about 8%. The reflectivity is clearly defined by SilecsRXC53〇, psT5〇&psT9〇, second layer, second layer And the three-layer anti-reflective coating composed of the third layer is reduced. In order to reduce the reflectance by adjusting the optical phase, the optical thickness (physical thickness X refractive index) of the three-layer structure is designed to be 0.253⁄4, 〇.5&amp ; and 〇.25λ〇(λ〇=550ηηι;). The film thickness and refractive index of the Silecs RXC 530, PST50 and PST90 obtained from the simulation software (Thin Film View, TOHO TSUSHO INC) are 103.6 for the FEA glass, respectively. Nm and 丨·3丨3, 丨2〇nm and 丨8 i, 63 〇4nm and 1.64. For PMMA substrates, the film thickness and refractive index of SilecsR XC 530, PST50 and PST90 are respectively l〇 3.6 nm and 1.313, 120 nm and 1.8 b and 63.04 nm and 1.64. The film thickness and reflectance of this experiment are shown in the inset of Figure 12. The film thickness and refractive index of this experiment for lecsRXC 530, PST50 and PST90 are l〇5.8nm and 1.313, 198.5nm and 1.94, 56nm and 1.84 for FEA glass substrates, respectively. For PMMA substrates The films of SilecsR XC 530, PST50 and PST90 have a thickness of 21 201238758 and refractive indices of 1〇3.6nm and 1.313, 120nm and 〗 814, 63.04nm f 1.64. These results show that for film thickness and refraction The experimental values of the rate and average reflectance are quite close to the theoretical values, and the good reproducibility of FEA glass and PMMA. As shown by circle 12, the inverse of the AR coating on the glass and PMMA substrates is G·356 and G.495%. The obtained reflectivity is significantly lower than that of i and PMMA substrates. The hardness of the surface of the anti-anti-machine layer of the anti-machine layer is 2 min for the kiss and lkg贞 respectively. The adhesive properties of the mixed film and the substrate (FEA glass and PMMA) are respectively as described in the rib 9 and the viscera 9 standard. The mixed film prepared by the method should be hardness and adhesion to the potential fresh device. Sex. / Recording surface [Table 3]

ΪIn view of the above, in the present invention, the mixed polyimide obtained by using the soluble carboxylic acid end group has an excellent thermal ancient multilayer anti-reflective coating, and the mixed film having the superior is made in the optical device. Bribe towel. Surface hardness and adhesion can be utilized [Simple description of the diagram] 22 201238758 Figure 1 illustrates the FTIR spectra of PI and PI/SiO 2 -TiO 2 films on double polished tantalum wafers. Figure 2 illustrates the change in viscosity and shear stress with shear rate for PST0-PST50 and SiO2-Ti02 core-shell solutions. Figure 3 illustrates the Raman spectrum of PI and PI/SiO 2 -Ti02 mixed films. Figure 4 shows XRD patterns of powders prepared from polyimide (PST0), polyimide/SiO 2 -Ti02, and pure Si〇2_Ti〇2 (PSTl®) films. Fig. 5 shows a hrtem image of a SiOrTi〇2 core-shell nanoparticle film coated on a tantalum wafer and treated by a hydrothermal process, and a corresponding electron diffraction pattern. Figure 6 shows the volume fraction size distribution of colloidal oxime 2 and SiOrTi〇2 core-shell solution obtained by dynamic light scattering (dls) method. Fig. 7 shows an FE-SEM micrograph of the prepared polyimine/SiOrTiO 2 mixed film. Figure 8 shows the afM diagram of the PST10, PST30 and PST50 hybrid films. Figure 9 illustrates the TGA curve of the 6FDA-6FPDA-COOH (PSTO) and polyimine/Si〇2_Ti〇2 blends PST10-PST50 at 1 (heating rate of TC/min' in a nitrogen stream. - * Figure 10 The transmittance of the visible film of PST0 and PST10-PST100 mixed film is shown. Fig. 11 shows the change of refractive index and the extinction coefficient of the PST0, PST100 and PST series mixed films at a wavelength of 3〇〇-80〇nm. Figure 12(8) And (b) the light reflection spectrum of the three-layer anti-reflection film on the FEA glass and the PMMA substrate, respectively.

Claims (1)

201238758 VII. Scope of Application for Patenting·· 1. Kind of glutamic acid and oxidized stone _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ And a cerium oxide-titanium oxide core-shell nanoparticle unit represented by the following formula (Π), wherein the weight ratio of the carboxyl group represented by R in the formula 1 to the OH in the formula (Π) and Ti is ' Polyimide. Oxidized oxide oxide • Titanium oxide core-shell nanoparticles in the range of 10:90 to 90:1〇: (I) • In the above, 'R represents a carboxyl group (-COOH), and Ar, Ar, and Ar may be the same or different and each represents a phenyl, anthracene, a phenyl group, and a group thereof (wherein X represents a Halogen substituted Cl_4 alkyl, phenyl_〇, _〇_, _c〇f, -S-, -SO- or -S〇r), m represents a value from ! to 30; 2. For example, a mixed film of soluble polyimine and cerium oxide-titanium oxide nano-nanoparticles in the first aspect of the patent range, wherein m is 2 to 1 in the polyimine of formula 1 The value. 3. A mixed film of a soluble polyimine and a cerium oxide-titanium oxide core or a nanoparticle according to the first aspect of the patent application, wherein the cerium oxide-titanium oxide core represented by the formula (11) is provided in the nanoparticle, · The weight ratio of oxidized stone to titanium oxide is in the range of 1: 8 25 . 24 201238758 4· A method for producing a mixed film of cerium oxide-titanium oxide core-shell nanoparticle according to any one of claims 1-3 to 3, comprising the following steps (a) under acidic conditions, The titanium oxide is coated with oxygen to obtain oxygen, and the oxygen is used to obtain the oxidized stone and the titanium oxide core-shell nanoparticle, wherein the oxidation: The amount of titanium oxide used is such that the oxidized dream after hydrolysis is in the range of 1:8 to 1:25; and (b) the polyimine having a carboxylic acid group and the step (a) are obtained. The cerium oxide is oxidized, and the core-shell nanomolecules are mixed in the range of 90:10~1〇··90 by weight ratio of 90:10~1〇··90 by coating method on a substrate by coating method. Coating and heating is carried out by using a carboxylic acid group contained on the polyimine and a hydroxyl group carried on the oxo-titanium oxide core-shell nanoparticle to carry out dehydration and esterification reaction to obtain a polyimine It is mixed with cerium oxide titanium oxide core-shell nanoparticle to form a thin film. 5. The method of manufacture according to claim 4, wherein the oxime oxidation of the step (8) is represented by the formula (Ti(OR') 4, wherein the ruth is c 6 straight or branched alkyl groups. The manufacturing method of claim 4, wherein the polyamidiamine having a carboxylic acid group used in the step (b) is an aromatic diamine and an aromatic dicarboxylic anhydride, molar equivalent/diamine molar equivalent After tbA is carried out, an acid anhydride is opened to obtain a polyamic acid having an acid anhydride group at the end, and then an acid anhydride group is reacted with an aromatic amine containing a carboxylic acid to obtain a polyamine having a carboxylic acid group at the terminal. The acid is subsequently subjected to hydrazine imidation to obtain a polyimine having a carboxylic acid group. 7. The method for producing a carboxylic acid group according to claim 4, wherein the dehydration reaction of the step (9) is in multiple stages. Baking is carried out. 25