JP4822311B2 - Method for producing siloxane-based composite compound - Google Patents

Description

  The present invention relates to a method for producing a composite compound of a fullerene and a siloxane compound that are widely used as an optical limiting material.

Fullerene is a substance in which carbon atoms are covalently bonded like a soccer ball, and has properties such as radical scavenging and superconductivity. In addition, fullerene is an ultrafine particle having a π-electron conjugated structure, and thus has an optical limiting effect (nonlinear optical effect). Here, the optical limiting effect refers to a phenomenon in which the relationship between the electromagnetic field of strong laser light and the electronic polarization of a substance becomes nonlinear. The light limiting effect is expressed by the equation of polarization P (ω) induced in the substance by the photoelectric field E (ω) of Taylor's expansion approximation.

When the electric field is not so strong, the nonlinear polarization after the second term can be ignored, and the polarization P can be considered to be proportional to the electric field E, but the amplitude of the light is increased for a strong electromagnetic wave such as a laser beam. Since it is not proportional, nonlinear polarization after the second term cannot be ignored. The coefficient χ ⁽ⁿ⁾ of each term is referred to as an nth-order nonlinear susceptibility (n = 2 or more), and the nonlinear susceptibility increases as the π-electron conjugated system is larger according to Miller's law.

  Due to the nonlinearity of polarization as described above, the transmitted light intensity exhibits hysteresis with respect to the change in the incident light intensity. Such nonlinear optical materials are indispensable materials for future optical communication and optical information processing systems, and π-conjugated molecules and semiconductor ultrafine particles are attracting attention as promising nonlinear optical materials. On the other hand, application to nanocarbon molecules and nanopore adsorbents utilizing the shape of fullerene has also been studied (see Non-Patent Document 1). However, the solubility of fullerene in an organic solvent is low, and it is difficult to mix with a matrix phase such as an organic polymer or an inorganic polymer, which is an obstacle to application development of fullerene as a composite material (see Non-Patent Document 2). .

In order to complex fullerene, a method for introducing fullerene into a matrix phase by π-π interaction using π electrons of fullerene has been reported (see Non-Patent Document 3). Specifically, a method in which a fullerene adduct obtained by adding a condensed polycyclic hydrocarbon such as a naphthyl group to fullerene is uniformly dispersed in tetrafunctional silane by reacting with methyltriethoxysilane (MTES). It is. Also disclosed is a method of dispersing a fullerene adduct added with a silane coupling agent in a matrix phase composed of an inorganic polymer (see Non-Patent Document 4).
P. Innocenzi et al. J. et al. Sol-Gel. Sci. and Tech. , 19, 263-266 (2000) T.A. Gunji, M.M. Ozawa, Y .; Abe J.M. Sol-Gel. Sci. and Tech. , 22, 219-224 (2001) A. Kraus, M.M. Schneider, A.M. Gugel, K.M. Mullen, J.M. Mater. Chem. , 7 (5), 763-765 (1997) P. Innocenzi et al. J. et al. Non-Crystalline Solids. , 265, 68-74 (2000)

  However, the solubility of fullerenes and fullerene adducts and the miscibility with siloxane polymers are low, and the methods described in Non-Patent Documents 3 and 4 can be uniformly dispersed in the matrix phase, but the concentration of fullerene is Since it is only about 0.1%, the light limiting property of the composite compound obtained by these methods is low and not practical.

  In view of the above problems, in the present invention, a covalent bond is formed between fullerene and a siloxane network by preparing a fullerene-silyl derivative having improved solubility in an organic solvent by a hydrosilylation reaction between fullerene and alkoxyhydrosilane. An object of the present invention is to prepare a fullerene-siloxane composite compound having a high concentration of fullerene.

  The present invention specifically provides the following.

  (1) A hydrosilylation step in which fullerene and hydrosilane are hydrosilylated to form a fullerene-silyl derivative, and the fullerene-silyl derivative and tetrafunctional silane are hydrolyzed and polycondensed by polycondensation. And a process for producing a siloxane-based composite compound.

  (2) The method for producing a siloxane-based composite compound according to (1), wherein the hydrosilane is a trialkoxysilane, and the tetrafunctional silane is a tetraalkoxysilane.

  (3) The method for producing a siloxane-based composite compound according to (1) or (2), wherein a molar ratio of silicon to the fullerene (Si / fullerene) is 1000 to 10.

  (4) The method for producing a siloxane-based composite compound according to any one of (1) to (3), wherein the polycondensation step is a step performed by a sol-gel method.

  (5) The method for producing a siloxane-based composite compound according to any one of (1) to (4), wherein the polycondensation step is a step performed in a nitrogen atmosphere.

  According to the inventions of (1) to (5), it is possible to improve the solubility of fullerene in an organic solvent by providing the hydrosilylation step. Specifically, a fullerene-silyl derivative in which a part of the carbon-carbon bond of fullerene is substituted with silane is generated by a hydrosilylation reaction. This fullerene-silyl derivative has nine ethoxy groups. This part serves as a cross-linking point when the tetrafunctional silane undergoes a polycondensation reaction and allows cohydrolysis polycondensation to proceed. Therefore, fullerene can be uniformly dispersed in the siloxane network at a high concentration. It can be done.

  In the invention of (2), the hydrosilane is trialkoxysilane, whereby the fullerene-silyl derivative can be uniformly dispersed in the siloxane network at a high concentration. Among hydrosilanes, trisilylsilane (5 molecules), diphenylchlorosilane (mixture), and phenyldichlorosilane (4 molecules) can be used to produce a hydrosilylation reaction with fullerene, but when these substances are used, fullerene-silyl The hydrolysis rate of the chloro group of the derivative is very fast, and the fullerene silyl derivatives are combined with each other to cause precipitation. Therefore, it is preferable to add a trialkoxysilane composed of an ethoxy group that is slower than the hydrolysis rate of the chloro group. Among these, it is particularly preferable to use triethoxysilane.

  Furthermore, by using tetraalkoxysilane as the tetrafunctional silane, fullerene can be more uniformly dispersed in the siloxane network. Among tetraalkoxysilanes, it is more preferable to use tetraethoxysilane which is inexpensive, has good transparency, and has excellent heat resistance and weather resistance.

  In addition, in the invention of (5), since the polycondensation step is performed in a nitrogen atmosphere, water and catalyst can be discharged out of the system, so that fullerene-silyl derivatives are hydrolyzed by moisture in the atmosphere. , Can be prevented from gelling. In addition, when a gel is formed in the polycondensation step, aggregation of fullerene-silyl derivatives due to π-π interaction can be suppressed.

  As described above, according to the present invention, a fullerene-silyl derivative having improved solubility in an organic solvent can be produced by a hydrosilylation reaction between fullerene and alkoxyhydrosilane. In addition, a fullerene-siloxane composite compound containing fullerene in a high concentration can be prepared by reacting a fullerene-silyl derivative with a tetrafunctional silane.

  The present invention will be described in detail below.

The present invention includes a hydrosilylation step in which a hydrosilylation reaction between fullerene and alkoxyhydrosilane is performed. Here, “fullerene” is a general term for a group of spherical shell-like carbon molecules including C ₆₀ and C ₇₀ . In the present invention, any one of C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₀ , C ₈₂ , C ₈₄ , C ₈₆ , C ₈₈ , C ₉₀ , C ₉₂ , C ₉₄ , and C ₉₆ may be used. Is particularly preferably C ₆₀ . Here, “alkoxyhydrosilane” refers to a composition represented by the following chemical formula (1). Here, R ₁ to R ₃ are preferably each independently an alkyl group which may have a functional group or a substituent.

  Specifically, as the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group. And a straight chain, branched chain or cyclic alkyl group such as a group, t-pentyl group, isoamyl group and n-hexyl group. Moreover, examples of the alkyl group which may have a functional group include a silyl group substituted with an alkyl group or an aryl group, and an alkoxy group.

  Examples of the alkyl group which may have a substituent include an alkoxy group, a haloalkyl group, a haloalkoxy group, an unsubstituted or substituted aryl group, and an aralkyl group. As the alkoxy group, carbon such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-hexyloxy group, cyclohexyloxy group, etc. Examples thereof include linear, branched or cyclic alkoxy groups of 1 to 6. Examples of the haloalkyl group include those in which one or two or more hydrogen atoms of the above-described alkyl group are substituted with a halogen atom, such as a chloromethyl group, a chloroethyl group, a fluoromethyl group, a trifluoromethyl group, and the like. Can be mentioned. Examples of the haloalkoxy group include those in which one or two or more hydrogen atoms of an alkoxy group are substituted with the above-described halogen atoms, such as chloromethoxy group, chloroethoxy group, fluoromethoxy group, trifluoromethoxy group. Etc.

Among them, it is more preferable to use triethoxyhydrosilane in which R ₁ to R ₃ are ethyl groups.

  The hydrosilylation reaction is performed using a known method. The reaction temperature is preferably 0 to 50 ° C., more preferably near room temperature. The reaction pressure is not particularly limited, and is usually 0.5 to 2 atmospheres, but is more preferably performed under normal pressure. The reaction time is preferably 1 hour to 100 hours, usually 10 hours to 50 hours. Moreover, the reaction solvent can isolate | separate a product by general operation, such as distillation, extraction, chromatography, and recrystallization, after reaction.

  The solvent used in the hydrosilylation reaction is not particularly limited, but specifically, aliphatic hydrocarbons such as pentane, hexane, octane, nonane, decane, benzene, toluene, cumene, orthoxylene, metaxylene, paraxylene. An aromatic hydrocarbon such as mesitylene, ethylbenzene, and propylbenzene, and an ether solvent such as diethyl ether, tetrahydrofuran, and dimethoxyethane are preferable, and it is more preferable to use hexane or toluene. Further, it is more preferable to use a catalyst such as chloroplatinic acid hexahydrate.

Further, the present invention, C ₆₀ produced by a hydrosilylation process _- has a silyl derivative, a polycondensation step of polycondensing a tetrafunctional silane. Here, “tetrafunctional silane” refers to a composition represented by the chemical formula (2). Here, each of R ₄ to R ₇ is preferably independently an alkyl group which may have a functional group or a substituent. Specifically, it is preferable to use the same functional group as R ₁ to R _{3 included in the} alkoxyhydrosilane represented by the chemical formula (1).

  The hydrolysis and polycondensation reactions are performed using a known method in a nitrogen atmosphere. The reaction temperature is preferably 0 to 150 ° C., more preferably 50 to 100 ° C. The reaction pressure is not particularly limited, and is usually 0.5 to 2 atmospheres, but is more preferably performed under normal pressure. The reaction time is preferably 1 to 10 hours, usually 2 to 5 hours. Moreover, the reaction solvent can isolate | separate a product by general operation, such as distillation, extraction, chromatography, and recrystallization, after reaction.

The solvent used in the hydrolysis and polycondensation reaction is preferably a solvent that can sufficiently cause the hydrolysis of the C ₆₀ -silyl derivative and the tetrafunctional silane. Specifically, it is preferable to use water and hydrochloric acid in excess. As a result, gelation of C ₆₀ -silyl derivatives can be prevented, and a composite compound having high condensation stability in which C ₆₀ and the siloxane network are bonded at the sol stage can be obtained.

  Hereafter, the result of having examined about the effectiveness of the manufacturing method of the siloxane type complex compound concerning the present invention is shown.

_{<C 60} - Synthesis of Silyl Derivative>
First, a chloroplatinic acid ethanol solution was added to a toluene solvent as a catalyst, dried over calcium sulfate, C ₆₀ and triethoxysilane (hereinafter referred to as TES) were added, and the reaction was performed at room temperature for 4 days. Subsequently, the catalyst was filtered and concentrated, and unreacted C ₆₀ was removed with diethyl ether, followed by concentration again to obtain a brown viscous liquid C ₆₀ -silyl derivative (hereinafter referred to as TES-C ₆₀ ). The yield at this time is about 30%, and the reaction scheme at this time is shown below.

Next, nuclear magnetic resonance (hereinafter referred to as NMR) and infrared absorption spectrum (hereinafter referred to as IR spectrum) of TES-C ₆₀ are shown in FIGS. In proton NMR of Figure 1, it has been shown that the signal to be attributed to the Si-H of the TES is lost in _{TES-C 60.} In the carbon NMR shown in FIG. 2, a signal attributed to C ₆₀ -H was observed. Further, the silicon NMR shown in Figure 3, it has been shown that signal TES is shifted downfield in _{TES-C 60.} Furthermore, in the IR spectrum shown in FIG. 4, absorption of Si—H stretching vibration and bending vibration disappeared in TES-C ₆₀ , and absorption of Si—C stretching vibration was newly confirmed. From the above results, it was shown that TES-C ₆₀ was synthesized by hydrosilylation of C ₆₀ and TES.

The TES-C ₆₀ was subjected to a fast atom bombardment mass spectrum (hereinafter referred to as FAB mass) measurement and an ultraviolet absorption measurement to examine the three-dimensional structure of TES-C ₆₀ . 5 to 8 are diagrams showing the results of the ultraviolet absorption measurement (hereinafter referred to as UV-VIS) of TES-C _60. FIG. FIGS. 6 and 8 show enlarged views around 430 nm in FIGS. 5 and 7, respectively. Molar extinction coefficient at the maximum absorption wavelength of C ₆₀ and _{TES-C 60} is 3500 in the _{TES-C 60,} are you lower than 56700 of _{C 60,} by TES are added to the _{C 60,} C _This is considered to be because the symmetry of ₆₀ was lowered.

In TES-C ₆₀ , when the concentration was increased, absorption not observed in C ₆₀ was observed around 435 nm. This _absorption, it was suggested that added TES 6-6 fused portion of the _{C 60} (see FIG. 8 parts enclosed). From these results and FAB mass measurement results, it was found that TES-C ₆₀ was obtained by adding three molecules of TES to C ₆₀ .

Furthermore, the solubility of TES-C ₆₀ was examined. 0.02 g of TES-C ₆₀ was weighed, a predetermined solvent was appropriately added, and the mixture was well stirred at room temperature, and the presence or absence of insoluble matter was visually confirmed. When insolubles were observed, the same operation was repeated with more solvent added. When the amount of the solvent necessary to dissolve 0.02 g of the sample was 1 ml or less, it was evaluated as easily soluble, soluble from 1 ml to 5 ml, soluble from 5 ml to 10 ml, and insoluble when 10 ml or more. The results are shown in Table 1. From this, it was shown that TES-C ₆₀ was dissolved in almost all organic solvents, and the solubility was remarkably improved as compared with C ₆₀ .

_{<C 60} - Synthesis of Silyl Derivative>
Tetraethoxysilane (hereinafter referred to as TEOS) was added to TES-C ₆₀ dissolved in ethanol while cooling with ice, and a mixture of water and a hydrochloric acid catalyst in a certain ratio was added dropwise. Then, after standing at room temperature for 10 minutes, a cohydrolysis polycondensation reaction was performed in an open system at 80 ° C., a nitrogen flow rate of 360 ml / min, a stirring speed of 150 rpm, and 4 hours. The obtained pale yellow high-viscosity sol (hereinafter referred to as PEOS-C ₆₀ sol) was diluted to 50% by mass with an ethanol solvent, cast into an acrylic petri dish, and then aged at 80 ° C. for about 7 days. Such a siloxane-based composite compound (hereinafter referred to as PEOS-C ₆₀ ) was prepared. The synthesis scheme at this time is shown below.

Was performed investigated the effect of changes in the molar ratio of _{C 60} to silicon in the _{PEOS-C 60} it gives. Samples in a state of varying the ratio of silicon to _{C 60,} with _{PEOS-C 60} obtained by the above method.

The results are shown in Table 2. From this yields the molar ratio of C ₆₀ increases is reduced to silicon, the weight average molecular weight was shown to be significantly increased. From this, it was suggested that TES-C ₆₀ became a crosslinking point and hydrolysis polycondensation progressed, and the crosslinking density of siloxane increased. Further, it was confirmed that the gels prepared from the obtained PEOS-C ₆₀ sol had a uniform aging period of about 7 days and changed from transparent to brown as the content of C ₆₀ increased. The molecular weight was measured by gel permeation chromatography (hereinafter referred to as GPC).

Next, the NMR spectra of PEOS and PEOS-C ₆₀ are shown in FIGS. In polyethoxysiloxane (hereinafter referred to as PEOS), only an ethoxy group signal was observed, but in PEOS-C ₆₀ , a signal attributed to the C ₆₀ -H bond was observed in the vicinity of 58.3 ppm. This signal is a signal derived from the C ₆₀ -H bond observed at 63.9 ppm of TES-C ₆₀ , and is shifted to the low magnetic field side in PEOS-C ₆₀ . This larger than the silicon electronegativity of carbon, silicon electron density C ₆₀ is increased because of donating electrons to C _60, presumably because a shift to the higher magnetic field side.

Next, silicon NMR of PEOS and PEOS-C ₆₀ sol is shown in FIG. The same sample as used in Table 2 was used as the sample. From the silicon NMR, the peak of the T structure, which is a unit structure of siloxane of PEOS-C ₆₀ , has a weak signal, and since the ratio of the T structure could not be calculated, only the Q structure is shown. Comparing PEOS and PEOS-C ₆₀ , PEOS-C ₆₀ showed that the signals due to the Q ² and Q ³ structures were shifted to the low magnetic field side. This is thought to be because the electronegativity of silicon is smaller than the electronegativity of carbon. In addition, since the Q ³ and Q ⁴ structures increase as the C ₆₀ content increases, the degree of siloxane condensation increases in the PEOS-C ₆₀ sol more than the homopolymerized PEOS sol, and the three-dimensional crosslinking occurs. It was suggested that it was composed of structures. From the results of FIGS. 9 to 11, it was shown that TES-C ₆₀ and TEOS are not a mixture but a copolymer.

Next, as a result of examining the solubility of PEOS and PEOS-C ₆₀ by the same method as described above, as shown in Table 5, the solubility was high in most organic solvents, but the concentration of C ₆₀ increased. As a result, it was shown that the solubility in hexane and chloroform decreased. This is thought to be due to the increase in molecular weight and the degree of crosslinking of siloxane.

Next, the results of studies on the condensation stability of PEOS-C ₆₀ are shown in FIGS. FIG. 12 is a graph showing the relationship between the storage time and the molecular weight when PEOS-C ₆₀ sol was prepared at 40% by mass by adding various solvents at a composition ratio of Si / C ₆₀ = 100 and stored at 0 ° C. It is the figure which showed the relationship. FIG. 13 is a graph showing the relationship between the storage time and the molecular weight when PEOS-C ₆₀ sol was prepared under the same conditions and stored at 20 ° C.

  From this, it was shown that the samples stored at 0 ° C. had good condensation stability with almost no change in molecular weight even after 60 days from the start of storage. On the other hand, in the sample stored at 25 ° C., when tetrahydrofuran is added (see THF Soln in the figure), the molecular weight is remarkably increased because tetrahydrofuran is a basic solvent. In addition, when comparing a sample to which no solvent was added (see “Neat” in the figure) and a sample to which ethanol was added (see “EtOH Soln.” In the figure), the sample without the solvent was more silanol group or ethoxy. It is thought that condensation occurred because the distance between the leaving groups of the group was small, and the molecular weight was increased.

FIG. 14 is a photograph of PEOS-C ₆₀ gel prepared from the obtained PEOS-C ₆₀ sol. As _{PEOS-C 60} gel content of _{C 60} is increased, changes from colorless to brown, both by [pi-[pi interaction _{C 60,} no aggregates of _{C 60, C 60} is uniformly dispersed the C _{60 -} siloxane complex compounds it was shown that were obtained.

The measurement equipment and measurement conditions used are as follows. JNM-ECP500 type manufactured by JEOL Ltd. was used for proton NMR and carbon NMR spectrum, and JMX-EX400 type made by JEOL Ltd. was used for silicon NMR spectrum. The Fourier transform infrared absorption (FT-IR) spectrum was measured by a carbon tetrachloride solution method using JIR-5300 type manufactured by JEOL. Spectra were obtained from 4000 cm ^-1 with a resolution of ^{4 cm -1} in the range of 250 cm ^-1. The fast atom bombardment mass (FABmass) spectrum was a The Mstation JMS 700 type manufactured by JEOL Ltd. The matrix was measured with m-nitrobenzyl alcohol.

  The ultraviolet-visible (UV-VIS) absorption spectrum was measured using a photodiode array spectrophotometer Multi Spec-1500 manufactured by Shimadzu Corporation. Moreover, Shimadzu Corporation LC-10Advp liquid feeding pump and RID-10A differential refractive index detector were used for the gel permeation chromatography (GPC). For the separation column, two 5 μ-Mixed D columns manufactured by Polymer Science Co., Ltd. were used in series. As the mobile phase, THF having a flow rate of 1.0 ml / min was used. For the calculation of molecular weight, a calibration curve was prepared using commercially available monodisperse polystyrene.

<Optical test>
[Examination of light limiting effect]
The light limiting effect of the PEOS-C ₆₀ gel was examined. The test was performed using an Nd: YAG laser (manufactured by Continium: 532 nm) capable of outputting a high energy laser (pulse width: 10 nsec, frequency: 10 Hz) in a short time.

  Specifically, the laser beam output from the Nd: YAG laser is reflected only by a double wave (wavelength: 532 nm, pulse width: 10 nsec, frequency: 10 Hz) by two matched mirrors, A high energy laser was used. Next, the high energy laser was transmitted through a lens (manufactured by Suruga Seiki Co., Ltd., focal length f = 10 cm) placed in front of the sample, and laser light having a beam diameter of 0.9 mm was incident on the sample. In addition, the transmitted light intensity was measured using a power meter (Laser power meter model AN / Z type manufactured by Offir), and the incident light intensity was changed by adjusting a switch.

The result is shown in FIG. In the PEOS gel film, the incident light intensity and the transmitted light intensity increased linearly at 90% transmittance according to Lambert-Beer's law. On the other hand, the PEOS-C ₆₀ hybrid gel film did not follow Lambert-Beer's law and exhibited a light limiting function. The transmittance of PEOS-C ₆₀ hybrid gel film containing C ₆₀ with S / C _{60 in the range} of 1000 to 10 decreases from 89% to 11%. When Si / C ₆₀ is 1000, the incident light intensity is 1163 mJ / cm ^2. When Si / C ₆₀ is 500, the incident light intensity is 990 mJ / cm ² , when Si / C ₆₀ is 300, the incident light intensity is 644 mJ / cm ² , when Si / C ₆₀ is 100, the incident light intensity is 534 mJ / cm ² , and Si / C _60. Is 50, the incident light intensity is 340 mJ / cm ² , and Si / C ₆₀ is 10, the incident light intensity is 130 mJ / cm ^{2. As} the C ₆₀ concentration increases, the threshold value of the incident light intensity and the saturated transmitted light intensity increase. Decreased to express the light limiting function.

<Mechanical test>
[Tensile test]
Next, the mechanical strength of the PEOS-C ₆₀ hybrid gel film was examined. A film having a thickness of 0.2 mm obtained by dissolving PEOS-C ₆₀ composite compound in ethanol so as to be 20% by mass and casting it into an acrylic petri dish and aging it at 80 ° C. for about 7 days was used. What was cut so that it might become 2 mm in width was used for the sample. This sample was measured using a tensile strength tester (TENSILON / UTM-II-20 type manufactured by Orientec Co., Ltd.) (crosshead speed 20 mm / min). The results are shown in Table 6.

From this higher the content of C ₆₀ is increased, increasing the tensile strength and Young's modulus, since the elongation rate is decreased, has been shown to be very hard material. As the content of TES-C ₆₀ serving as a crosslinking agent increases, the hydrolysis polycondensation of PEOS-C ₆₀ proceeds, the molecular weight increases, and the PEOS-C ₆₀ composite compound gel film has a three-dimensional crosslinked structure. Is suggested.

[Hardness measurement]
Next, the hardness measurement of the PEOS-C ₆₀ composite compound coating film was examined. A sample was prepared by diluting PEOS-C ₆₀ composite compound sol to 20% by mass with an ethanol solvent as a coating solution, and performing dip coating (once) on each organic substrate and inorganic substrate surface. The winding speed at this time is 80 mm / min. Thereafter, it was dried at 80 ° C. for 24 hours, and further dried at 100 ° C. for a predetermined time to prepare a coating film.

The adhesion of the coating film was measured by a grid pattern method according to JIS K5400. Cuts which penetrated the coating film on the test piece and reached the ground surface were made in a grid pattern (100 in 1 cm ² ). Next, a cellophane adhesive tape was applied onto the grids and lightly pressed to peel off. Thereafter, the number of the remaining coating film pieces was counted by visual observation and scored in the range of 0 to 10 points.

  Further, the pencil hardness of the coating film was measured by a handwriting method according to JIS K5400. After fixing the test piece on a horizontal table, hold the pencil at an angle of about 45 °, and push it forward 1 cm at a constant speed of about 1 cm / s while pressing it against the coated surface as hard as possible without breaking the core. I scratched the coating. Each time you scratch, the tip of the pencil core is sharpened anew, and the test is repeated 5 times with the same density symbol. The density symbol is one level lower than the pencil density symbol where the scratches on the paint film are 3 or more times. It was. For the measurement, Mitsubishi Pencil Uni (trade name) that has been inspected by the Japan Paint Association was used. The results at this time are shown in Table 7.

From this, it was found that the coating film showed good adhesion regardless of the type of substrate. In particular, it was shown that the inorganic substrate was cured earlier. This is probably because the silanol group of PEOS-C ₆₀ and the OH group on the surface of the inorganic substrate formed a metalloxane-type bond. Also from the results of the adhesion and the pencil hardness was found to have high adhesion and pencil hardness in accordance with the concentration of C ₆₀ is increased is obtained. The reason is considered to be that as the content of TES-C ₆₀ serving as a crosslinking agent increases, the hydrolysis polycondensation reaction proceeds, and the molecular weight increases and a three-dimensional crosslinked structure is formed.

Is a diagram showing the _{TES-C 60} and TES proton NMR results of. Is a diagram showing the _{TES-C 60} and TES carbon NMR measurement results of. Is a diagram showing the silicon NMR results of the _{TES-C 60} and TES. It is a view showing a result of IR measurement _{TES-C 60} and TES. Is a graph showing the UV spectra of _{TES-C 60} and TES. Is a graph showing the UV spectra of _{TES-C 60} and TES. Is a graph showing the UV spectra of _{TES-C 60} and TES. Is a graph showing the UV spectra of _{TES-C 60} and TES. It is the figure which showed the carbon NMR measurement result of PEOS. It is a view showing a carbon NMR measurement results of _{PEOS-C 60.} It is a diagram showing the _{PEOS-C 60} and PEOS silicon NMR results of. PEOS-C ₆₀ was added with various solvents is a diagram showing the relationship between the storage time and the molecular weight when stored under 0 ° C.. It is a diagram showing the relationship between the storage time and the molecular weight in the case of the PEOS-C ₆₀ was added to various solvents and stored under 20 ° C.. Is a diagram showing the _{PEOS-C 60} gel prepared from _{PEOS-C 60} sol. It is a diagram showing the optical limiting effect of _{PEOS-C 60} gel prepared from _{PEOS-C 60} sol.

Claims (4)

Hydrosilylation of fullerene and hydrosilane to produce a fullerene-silyl derivative;
The fullerene - silyl derivative, and a tetrafunctional silane, a hydrolyzed possess a polycondensation step of polycondensing the,
A method for producing a siloxane-based composite compound , wherein the polycondensation step is performed under a nitrogen stream .   The method for producing a siloxane-based composite compound according to claim 1, wherein the hydrosilane is a trialkoxysilane, and the tetrafunctional silane is a tetraalkoxysilane.   The method for producing a siloxane-based composite compound according to claim 1 or 2, wherein a molar ratio of silicon to the fullerene is 1000 to 10. The method for producing a siloxane-based composite compound according to any one of claims 1 to 3 , wherein the polycondensation step is performed by a sol-gel method.

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