JP5176272B2 - Method for producing particulate metal oxide derivative - Google Patents

Description

  The present invention relates to a method for producing a metal oxide derivative that is excellent in uniform dispersibility and can obtain high mechanical properties by improving the miscibility with a matrix resin in forming a composite material with a resin such as a polycarbonate resin (PC resin). About.

  It is widely known that various members of an automobile are made of resin, thereby contributing to the weight reduction of the member and the automobile. Recently, the role of resinization for weight reduction is large, such as the application of a polyamide-based material for the main purpose of weight reduction even in an automobile outer panel where a copper plate has been used so far. In addition to the outer panel, there is an increasing trend to replace the metal material with the resin material, such as changing the fuel tank from the conventional steel plate to a resin hollow container made mainly of polyethylene.

  However, on the other hand, in the glass member such as a windshield, the present state is that the resin is hardly progressed. Although the transparency and impact resistance of glass have already been obtained with polycarbonate resin, the amount of resin expansion (for example, linear expansion coefficient) with respect to heat is extremely large compared to that of glass, and the bending rigidity of glass Since it is inferior, resin replacing glass is not generally obtained.

  In order to reduce the amount of thermal expansion, reinforcement with glass fibers or the like is known, but in order to ensure transparency, a non-reinforced resin must be selected. That is, the present situation is that a resin having transparency, small thermal expansion, and high rigidity has not been obtained.

  On the other hand, as a technique for improving various physical properties of the resin, while maintaining the flexibility, low density, moldability, etc., which are the characteristics of the resin, the high strength, high elastic modulus, heat resistance, electrical characteristics, etc., which are the characteristics of the inorganic compound As a method for improving such physical properties, composite materials using nano-order level inorganic fine particles instead of conventional glass fiber and talc-reinforced resins, so-called polymer nanocomposites, have been developed. Has been attracting attention. Examples of such composite materials include “composite materials and methods for producing the same (Patent No. 2519045 / Toyota Chuken)” and “polyamide composite materials and methods for producing the same (Japanese Patent Publication No. 7-47644 / Ube Industries, etc.)”, “Polyolefin composite materials and production methods thereof (Japanese Patent Laid-Open No. 10-30039 / Showa Denko)” and the like.

  In any case of polymer nanocomposites using nano-order level inorganic fine particles as described above, improving the dispersibility of fine inorganic fine particles is one of the major points of improving physical properties, and the dispersibility of inorganic fine particles is highly efficient. In order to improve at low cost, various dispersion methods have been studied and proposed.

  A kneading method is mentioned as one means of such a dispersion method. The above-mentioned Japanese Patent Publication No. 7-47644 and Japanese Patent Laid-Open No. 10-30039 correspond to melt kneading a molten polymer and nano-order inorganic fine particles using a kneader or the like. Further, as a method for further improving the dispersibility in the kneading method, a layered clay is dispersed in a polar solvent, and this is brought into contact with the polymer in a molten state. And “resin composition and manufacturing method thereof (JP 2000-53871 / Toray)” in which a supercritical fluid is brought into contact with inorganic fine particles and a polymer during kneading have been proposed.

  Although these methods improve the dispersibility to some extent at a relatively low cost by modifying inorganic fine particles and polymers, adding a solvent and a supercritical fluid during kneading, etc., sufficient dispersibility is still obtained. It is difficult to say that the cost of improving physical properties is sufficient. In addition, when this method is applied to polycarbonate resin, which is attracting attention as a substitute for glass, since inorganic fine particles are generally hydrophilic, dispersion in the resin is poor and aggregation occurs, and fine particles below visible light are used. The result is that the transparency inherent in the resin is impaired.

  For these reasons, attempts have been made to increase the dispersibility by using a silane coupling agent for the inorganic fine particles, and the dispersibility has not been obtained. Is the current situation. In general, a silane coupling agent has a short molecular chain and can be attached to the surface of inorganic fine particles, but it does not have sufficient interaction force to develop miscibility with the resin, so it is miscible with the resin. Is low and uniform dispersion is difficult. Those having a long molecular chain are generally difficult to obtain, and due to their length, the reactivity with inorganic fine particles is low, and the reaction amount is extremely small, so that a sufficient effect cannot be obtained.

  In “resin window and manufacturing method thereof (Japanese Patent Laid-Open No. 11-343349)”, a method is described in which a polymer is dissolved in a solvent, the polymer solution and inorganic fine particles dispersed in the solvent are sufficiently mixed, and then the composite is precipitated. However, even in this method, it is inevitable that a part of the inorganic fine particles is aggregated, and high transparency has not been obtained. This suggests that the surface modification of the inorganic fine particles is insufficient.

  In particular, when paying attention to the composition of polycarbonate, as a method of synthesizing a polycarbonate-silica composition having excellent dispersibility, an alkoxysilyl group introduction technique “organic-inorganic hybrid polymer material and its production method (specially Kaihei 11-209596, Japanese Patent Laid-Open No. 11-255883 / Orient Chemical). This technology is epoch-making in that silica can be dispersed in the nano-order in polycarbonate by adjusting the amount of tetraalkoxysilane introduced, but the synthesis of raw materials is expensive and the resulting material is thermosetting. The use is remarkably limited in that it is a composition and cannot be freely molded.

  Further examples of other dispersion methods for polycarbonate compositions include the work by Huang et al., Akron University. (“Synthesis of Polycarbonate-Layered Silicate Nanocomposites via Cyclic Oligomers, M Huang,.; Lewis, S .; Brittain, WJ; Vaia, RAMacromolecules 2000, 33, p. 2000-2004) This technology is a composite of polycarbonate and layered compounds. The lack of dispersibility in obtaining the resin was overcome by using a polycarbonate cyclic oligomer, and after the polycarbonate cyclic oligomer was kneaded with the layered oxide, the oligomer was subjected to ring-opening polymerization, thereby realizing high dispersibility and physical properties. However, since the cyclic oligomer of polycarbonate as the main raw material cannot be produced at low cost, it is extremely disadvantageous industrially.

  As a recent technology of polycarbonate nanocomposites, “Polycarbonate resin composition, molded article comprising the same, and surface-treated fine silica obtained by sol-gel method in the presence of surfactant and compounded in polycarbonate” Method (Japanese Patent Application Laid-Open No. 2004-107470 / Teijin), but the transparency is maintained only with a thin film of about 10 microns, and the transparency does not reach a satisfactory level at a thickness of 1 mm or more.

  As described above, many studies have been made on a method for producing a nanocomposite in which inorganic fine particles are dispersed, but a decisive method has not yet been established, and in particular, a reduction in transparency and thermal expansion in a polycarbonate resin. Further study on the improvement of rigidity is necessary.

Patent No. 2519045 Japanese Patent Publication No.7-47644 JP-A-10-30039 JP-A-11-310643 JP 2000-53871 A JP-A-11-343349 JP-A-11-209596 JP-A-11-255883 JP 2004-107470 A Lewis, S.; Brittain, W.J.; Vaia, R.A.Macromolecules 2000,33, p.2000-2004

  This invention is made | formed in view of such a conventional problem, and makes it a subject to obtain the inorganic microparticles | fine-particles of the nano order level which are excellent in the dispersibility to resin.

In order to achieve the above object, the present invention provides:
A first step of producing a particulate metal oxide solution containing a particulate metal oxide ( A) having a hydroxyl group on the surface at a concentration of 30 to 70 wt%;
A second step of adding a metal compound (B) having one or more alkoxy groups to the particulate metal oxide solution to react with at least part of the surface hydroxyl groups of the particulate metal oxide (A). When,
A third step of mixing the metal compound (B) and the compound (C) having chemical binding ability with the particulate metal oxide solution, and reacting with at least a part of the metal compound (B);
The equipped,
The metal compound (B) has in addition to the epoxy groups of the one or more alkoxy groups, the compound (C) is characterized polycarbonate resin der Rukoto having terminal hydroxyl groups, particulate metal oxide The present invention relates to a method for producing a derivative. The present invention also includes a first step of preparing a particulate metal oxide solution containing a particulate metal oxide (A) having a hydroxyl group on the surface at a concentration of 30 to 70 wt%,
A second step of adding a metal compound (B) having one or more alkoxy groups to the particulate metal oxide solution to react with at least part of the surface hydroxyl groups of the particulate metal oxide (A). When,
A third step of mixing the metal compound (B) and the compound (C) having chemical binding ability with the particulate metal oxide solution, and reacting with at least a part of the metal compound (B);
With
The metal compound (B) has an amino group in addition to the one or more alkoxy groups, and the compound (C) is a polycarbonate resin having an epoxy group at a terminal. The present invention relates to a method for producing a product derivative.

  The inventors of the present invention have intensively studied to achieve the above object. As a result, according to the procedure described above, the metal compound (B) represented by the silane coupling agent is bonded as the first step to the surface of the particulate metal oxide (A) as the inorganic fine particles, and the metal compound ( B) a metal having high chemical compatibility with general-purpose resins by binding a compound (C) having a terminal structure having high chemical compatibility with B) and high compatibility with the resin to be blended. Found that an oxide derivative can be obtained

  Therefore, by blending the obtained metal oxide derivative in a predetermined resin, the filling effect as an inorganic filler of the particulate metal oxide (A) constituting the metal oxide derivative, and the particles Excellent mechanical properties such as elastic modulus and low linear expansion (linear expansion coefficient) due to a synergistic effect with the uniform dispersion of the metal oxide derivative containing the metal oxide (A), and excellent transparency A resin composition can be obtained.

  As is clear from the above contents, the metal compound (B) functions as a mediating compound that mediates the metal oxide (A) and the compound (C).

  As described above, according to the present invention, metal oxide (metal oxide derivative) particles having high miscibility with a resin can be provided. Therefore, the metal oxide particles can be uniformly dispersed in the resin, and provide a resin composition having excellent mechanical properties such as a low coefficient of linear expansion and a high elastic modulus while maintaining the transparency of the resin. can do.

  Hereinafter, other features and advantages of the present invention will be described in detail based on the best mode for carrying out the invention.

(Particulate metal oxide (A))
The particulate metal oxide (A) used in the present invention needs to be a metal oxide having a hydroxyl group on a part of its surface. The hydroxyl group is an indispensable functional group because it becomes a reactive base point with the metal compound (B) described later.

  Although the said particulate metal oxide (A) is not specifically limited, For example, metal oxides, such as a silica, an alumina, and a hematite, can be illustrated. The reason for using such an oxide is to utilize the fact that it is chemically stable and has no reactive sites other than the above-mentioned hydroxyl groups. These test forms may be in a powdered state or in a colloidal state dispersed in water or the like. However, since significant aggregation may occur by making the powder state, it is dispersed in water or the like. It is preferable to select the colloidal state.

  As described above, the metal species is not particularly limited as long as it has a hydroxyl group. However, if the purpose is to disperse the finally obtained derivative in the resin, the property of deteriorating the resin is extremely small. It is preferable to select silicon and aluminum that are inexpensive in terms of cost, and examples of such representative compounds include silica and boehmite (monoalumina monohydrate).

  There is no particular limitation on the particle shape of the particulate metal oxide (A). In the case of silica, a sphere is generally known and can be selected. Various types of boehmite are known. Any of a plate shape and a needle shape can be applied. The shape other than the sphere is not particularly limited and can be appropriately selected. As is known from the Halpin-Tsai equation, it is desirable to select particles having an aspect ratio rather than a sphere, considering that particles having a higher aspect ratio can obtain higher mechanical properties.

  Moreover, there is no limitation in particular about the magnitude | size of the said particulate metal oxide (A), According to a desired physical property, it can select arbitrarily. If the derivative finally obtained is mixed with a resin having transparency, the size needs to be several nanometers to several tens of nanometers. According to the inventors' investigation, when a spherical metal compound is used as a starting material, the diameter is 10 to 20 nanometers, and when a needle-like metal compound is used as a starting material, the cross-sectional diameter is several nanometers and length. Even if the direction was 50 to 200 nanometers, it was possible to obtain one that maintained sufficient transparency.

(Metal compound (B))
As described above, the metal compound (B) functions as a mediating compound that mediates the particulate metal oxide (A) and the compound (C), and the hydroxyl group of the particulate metal oxide (A). It is necessary to have one or more alkoxy groups for reacting with and chemically bonding. The number of alkoxy groups that the metal compound (B) has is not particularly limited.

In addition, as long as it has one or more alkoxy groups, there are no particular limitations on the other functional groups, but from the viewpoint of reactivity with the compound (C) described later, the chemical bonding ability with the compound (C) is improved. It is preferable to have a terminal functional group, and in this case, the reactive base point of the compound (C) can be appropriately selected as described later. In particular, it has an epoxy group or an amino group in terms of reactivity .

  In the case of selecting a silane coupling agent as the metal compound (B), there are three examples of alkoxy groups that satisfy the above, (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxy) (Cyclohexyl) ethyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Two examples of silane and alkoxy groups are (3-glycidoxypropyl) methyldimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. An alkoxy group is one example (3-glycidoxypropyl Dimethyl silane, 3-aminopropyldimethylethoxysilane can be exemplified.

  In addition to the silane coupling agent, a titanium coupling agent and an aluminum coupling agent can be selected. The metal element in the coupling agent can be appropriately modified depending on the metal atom constituting the particulate metal oxide (A).

(Compound (C))
The compound (C) used in the present invention needs to be appropriately selected depending on the terminal structure of the metal compound (B). For example, if the metal compound (B) has a terminal amino group structure such as 3-aminopropyltrimethoxysilane described above, the compound (C) reacts with an amino group such as an epoxy group or a carboxyl group. It is necessary to select a compound having a terminal structure. As another example, if (B) has a terminal epoxy group structure such as (3-glycidoxypropyl) trimethoxysilane described above, it reacts with an epoxy group such as an amino group, a carboxyl group, or a hydroxyl group. It is necessary to select a compound having a terminal structure.

  In particular, from the viewpoint of easy availability and reactivity, as a combination of terminal functional groups of the metal compound (B) / compound (C), an amino group / epoxy group, an epoxy group / amino group, an epoxy group / carboxyl group, The epoxy group / hydroxyl combination is preferred.

  In the compound (C), the structure other than the functional group that reacts with the metal compound (B) is not particularly limited. However, in order to improve the dispersibility of the nanoparticles in the matrix resin, which is the object of the present invention, and to improve the physical properties of the resulting composite, it is essential to increase the miscibility with the resin.

As one of the techniques, for example, when polycarbonate is selected as the matrix resin of the resin composition, the compound (C) is a polycarbonate resin derivative . In this case, for example, if the metal compound (B) has a terminal epoxy group structure such as (3-glycidoxypropyl) trimethoxysilane described above, a polycarbonate resin having a terminal hydroxyl group is used as the derivative. be able to. In this case, the metal compound (B) and the compound (C) are bonded through a reaction between the hydroxyl group and the epoxy group.

Further, for example, if the metal compound (B) has a terminal amino group structure such as the above-mentioned 3-aminopropyltrimethoxysilane, the compound (C) is a polycarbonate resin (derivative) whose terminal is modified with an epoxy group. At least one of the above is used . In this case, the metal compound (B) and the compound (C) are bonded through a reaction between the amino group and the epoxy group.

(Addition and reaction of particulate metal oxide (A) and metal compound (B))
In the present invention, when the particulate metal oxide (A) and the metal compound (B) are reacted, the particulate metal oxide (A) is blended in a predetermined solvent, and a high concentration of 30 to 70 wt% is obtained. After preparing the particulate metal oxide solution, the metal compound (B) is added to the solution.

  If the concentration of the particulate metal oxide (A) is less than 30 wt%, the concentration of the reaction base point in the reaction field is low, so that a sufficient amount of reaction cannot be secured, and low in the system due to condensation polymerization between the metal oxides (B). May lead to an increase in molecular by-products. In particular, when the metal compound (B) having a long-chain functional group is to be reacted in order to improve the dispersibility in the resin, which is the object of the present invention, the reaction amount is significantly reduced due to the large steric hindrance. . On the other hand, when the concentration of the particulate metal oxide (A) exceeds 70 wt%, the particulate metal oxide (A) and the metal compound are caused by an extreme increase in the viscosity of the particulate metal oxide (A). Mixing / stirring with (B) becomes insufficient, the diffusion of both components becomes insufficient, and the reaction amount may rather decrease. More preferably, the range of 40 to 60 wt% is good.

  As described above, the particulate metal oxide solution containing the high concentration particulate metal oxide (A) can be prepared by a sol-gel method, a hydrothermal synthesis method, or the like. In addition, when the particulate metal oxide (A) is obtained in a solution state from the production stage, the production condition is such that the product has a high concentration, or the low concentration is concentrated by heat drying or ultrafiltration. do it.

  There is no particular limitation on the type of solvent constituting the particulate metal oxide solution. An alcohol solvent such as isopropyl alcohol, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an ether solvent such as tetrahydrofuran, an aromatic solvent such as toluene, and water can be selected, and a mixed solvent thereof can also be used. However, the particulate metal oxide (A) can be satisfactorily dispersed even when the surface is not modified, and is represented by, for example, silica produced by the water glass method and boehmite produced by the hydrothermal synthesis method. As described above, many products are obtained in the form of water-dispersed sol at the production stage. In general, water is particularly preferable because the water-dispersed sol is inexpensive and easily available.

  The bond between the particulate metal oxide (A) and the metal compound (B) is the surface hydroxyl group of the particulate metal oxide (A) and the alkoxy group of the metal compound (B) or the hydrolysis thereof. This is caused by a polycondensation reaction between the hydroxyl groups.

  Moreover, the reaction conditions of the particulate metal oxide (A) and the metal compound (B) in the particulate metal oxide solution are not particularly limited. For example, when silica dispersed in methyl ethyl ketone is used as the particulate metal oxide (A), the metal compound (B) (for example, silane coupling) is prepared while a reflux condenser is attached to the reaction vessel to prevent drying by evaporation of the solvent. After adding an appropriate amount of the agent, the mixture is stirred at 70 ° C. to obtain a reaction product of the particulate metal oxide (A) and the metal compound (B). The reaction temperature is preferably as high as possible from the viewpoint of reactivity. However, since the contact frequency of the particles is increased due to boiling, and suspicion is likely to occur, the temperature is lowered by 5 to 10 ° C. from the boiling point of the solvent. Is preferred.

(Reaction of metal compound (B) and compound (C))
After the particulate metal oxide (A) and the metal compound (B) are reacted as described above, the metal compound (B) and the compound (C) are reacted, and the particulate metal oxide (A ) To the compound (C) via the metal compound (B).

  The conditions for reacting the compound (C) with the metal compound (B) are not particularly limited. For example, in the case of using a methyl ethyl ketone dispersion solution of the particulate metal oxide (A) obtained by reacting the metal compound (B) described above, a reflux condenser is attached to the reaction vessel to prevent drying by evaporation of the solvent. The compound (C) is added to the particulate metal oxide (A) via the metal compound (B) by adding the epoxy resin as the compound (C) and reacting at 100 ° C. with stirring. Can be combined. The reaction temperature is preferably as high as possible from the viewpoint of reactivity, but is preferably in the range of 70 to 130 ° C. because the terminal functional group of the compound (C) is easily modified.

  The particulate metal oxide (A) and the metal compound in the particulate metal oxide solution are mixed with the compound (C) for the same reason as in the case of the particulate metal oxide solution described above. It is preferable that the concentration of the reaction product with (B) is in the range of 30 to 70 wt%.

  In the above example, the compound (C) is directly mixed with the particulate metal oxide solution containing the particulate metal oxide (A) and the metal compound (B). However, when the solubility of the compound (C) in the particulate metal oxide solution is low, the compound (C) is uniformly mixed in the particulate metal oxide solution and dissolves the compound (C). It is also possible to separately prepare a solvent capable of producing a solution, dissolve the compound (C) in this solvent to form a solution, and then add this solution to the particulate metal oxide solution.

  In addition, the reaction product of the particulate metal oxide (A) and the metal compound (B) is extracted from the particulate metal oxide solution using centrifugal separation or the like, and this is a solvent having solubility in the compound (C). It is also possible to add and mix the compound (C) after dissolving and dispersing again. Also in this case, for the same reason as described above, the concentration of the reaction product of the particulate metal oxide (A) and the metal compound (B) in the obtained solution after being redissolved in the solvent is 30 to 70 wt. % Range is preferable.

  Examples are given below, but the present invention is not limited thereto.

Reference example 1
(First step: Preparation of particulate metal oxide (A) solution)
100 mL of methyl ethyl ketone-dispersed colloidal silica (MEK-ST) manufactured by Nissan Chemical Industries, Ltd. was heated and concentrated under reduced pressure to obtain a dispersion solution having a silica solid content of 40 wt%.
(Second step: Reaction of metal compound (B))
To the above solution, 30 ml of (3-glycidoxypropyl) trimethoxysilane (Silaace S510, hereinafter referred to as 3GPTMS) manufactured by Chisso Corporation was added and stirred and refluxed at 70 ° C. for 24 hours.
(Third step: Reaction of compound (C))
1 g of terephthalic acid manufactured by Aldrich Japan Co., Ltd. was added to the reaction solution, and the mixture was stirred and refluxed at 100 ° C. for 24 hours.

Reference example 2
Particles were produced in the same procedure except that 1 g of terephthalic acid in the third step of Reference Example 1 was replaced with 1 g of hexamethylenediamine.

Example 1
Particles were produced in the same procedure except that 1 g of terephthalic acid in the third step of Reference Example 1 was replaced with 5 g of a polycarbonate resin having an average single-terminal hydroxyl group (polystyrene equivalent weight average molecular weight = 20000).

  In addition, the polycarbonate of an average one-terminal hydroxyl group introduces a hydroxyl group by adding bisphenol A (equimolar to polycarbonate) and an alkali metal catalyst to a polycarbonate produced by the interface method.

Reference example 3
Replacing 3GPTMS in the second step of Reference Example 1 with 3-aminopropyltrimethoxysilane (Syra Ace S360, hereinafter referred to as 3APTMS) manufactured by Chisso Corp. Epicoat 1010) Particles were produced in the same procedure except for 1 g.

Example 2
Particles were processed in the same procedure except that 3GPTMS in the second step of Reference Example 1 was changed to 3APTMS and 1 g of terephthalic acid in the third step was changed to 5 g of polycarbonate having an average single-terminal epoxy group (polystyrene equivalent weight average molecular weight = 20000). Manufactured.

  In addition, the polycarbonate of the average one terminal epoxy group introduces an epoxy group by adding equimolar amount of bisphenol A monoglycidyl ether to the polycarbonate in the terminal sealing step of the polycarbonate prepared by the interfacial method.

Example 3
(First step: Preparation of particulate metal oxide (A) solution)
30 g of boehmite alumina (CAM9010) manufactured by Sakai Kogyo Co., Ltd. was dispersed in water to obtain a dispersion solution having a boehmite solid content of 60 wt%.
(Second step: Reaction of metal compound (B))
30 ml of 3GPTMS was added to the above solution and stirred and refluxed at 90 ° C. for 24 hours.
(3rd process: Reaction of compound <C>)
5 g of polycarbonate resin having an average hydroxyl group at one terminal (weight average molecular weight in terms of polystyrene = 20000) was dissolved in 20 ml of tetrahydrofuran, added to the above reaction solution, and stirred and refluxed at 120 ° C. for 24 hours.

Example 4
(First step: Preparation of particulate metal oxide (A) solution)
30 g of boehmite alumina (CAM9010) manufactured by Sakai Kogyo Co., Ltd. was dispersed in water to obtain a dispersion solution having a boehmite solid content of 40 wt%.
(Second step: Reaction of metal compound (B))
30 ml of 3GPTMS was added to the above solution and stirred and refluxed at 90 ° C. for 24 hours. After the reaction, the surface-modified boehmite was separated by centrifugation and redispersed in tetrahydrofuran to obtain a dispersion solution having a boehmite solid content of 50 wt%.
(Third step: Reaction of compound (C))
5 g of a polycarbonate resin having an average hydroxyl group at one end (weight average molecular weight in terms of polystyrene = 20000) was added to the above solution, and the mixture was stirred and refluxed at 120 ° C. for 24 hours.

Reference example 4
Particles were produced in the same procedure except that 3GPTMS in the second step of Example 3 was replaced with 3APTMS and 5 g of the polycarbonate resin having an average one-terminal hydroxyl group in the third step was replaced with 1 g of epoxy resin (Ebicoat 1010).

Example 5
Particles were produced in the same procedure except that 3GPTMS in the second step of Example 4 was replaced with 3APTMS and 5 g of the polycarbonate resin having an average one-terminal hydroxyl group in the third step was replaced with 5 g of polycarbonate having an average one-terminal epoxy group.

Comparative Example 1-1
In the first step of Reference Example 1, particles were produced in the same procedure except that methyl colloidal silica (MEK-ST) was diluted with methyl ethyl ketone and the silica solid content concentration was changed to 10 wt%.

Comparative Example 1-2
Particles were produced by the same procedure except that the second step of Reference Example 1 was omitted.

Comparative Example 2-1
In the first step of Reference Example 2, particles were produced in the same procedure except that methyl colloidal silica (MEK-ST) was diluted with methyl ethyl ketone and the silica solid content concentration was changed to 10 wt%.

Comparative Example 2-2
Particles were produced by the same procedure except that the second step of Reference Example 2 was omitted.

Comparative Example 3-1
In the first step of Example 1 , particles were produced in the same procedure except that methyl colloidal silica (MEK-ST) was diluted with methyl ethyl ketone and the silica solid content concentration was changed to 10 wt%.

Comparative Example 3-2
Particles were produced in the same procedure except that the second step of Example 1 was omitted.

Comparative Example 4-1
In the first step of Reference Example 3 , particles were produced in the same procedure except that methyl colloidal silica (MEK-ST) was diluted with methyl ethyl ketone and the silica solid content concentration was changed to 10 wt%.

Comparative Example 4-2
Particles were produced by the same procedure except that the second step of Reference Example 3 was omitted.

Comparative Example 5-1
In the first step of Example 2 , particles were produced in the same procedure except that methyl colloidal silica (MEK-ST) was diluted with methyl ethyl ketone and the silica solid content concentration was changed to 10 wt%.

Comparative Example 5-2
Particles were produced in the same procedure except that the second step of Example 2 was omitted.

Comparative Example 6-1
In the first step of Example 3 , particles were produced by the same procedure except that the boehmite solid content concentration was changed to 10 wt%.

Comparative Example 6-2
Particles were produced in the same procedure except that the second step of Example 3 was omitted.

Comparative Example 7-1
Particles were produced in the same procedure except that the boehmite solid content concentration was changed to 10 wt% in the first step and the second step of Example 4 .

Comparative Example 7-2
In the first step of Example 4 , 30 g of boehmite alumina (CAM9010) was dispersed in tetrahydrofuran, and particles were produced in the same procedure except that the second step was omitted.

Comparative Example 8-1
In the first step of Reference Example 4 , particles were produced by the same procedure except that the boehmite solid content concentration was changed to 10 wt%.

Comparative Example 8-2
Particles were produced in the same procedure except that the second step of Reference Example 4 was omitted.

Comparative Example 9-1
Particles were produced in the same procedure except that the boehmite solid content concentration was changed to 10 wt% in the first step and the second step of Example 5 .

Comparative Example 9-2
In the first step of Example 5 , 30 g of boehmite alumina (CAM9010) was dispersed in tetrahydrofuran, and particles were produced in the same procedure except that the second step was omitted.

(Measurement of reforming amount)
About said Example , reference example, and a comparative example, the surface modification amount was measured in the following procedure.
-Centrifugate the obtained dispersion solution of each particle and take out the solid content of the settled particles.
-Disperse this in tetrahydrofuran and centrifuge again to remove the solid particles that settle. Return this to 3 lines. The unreacted modifier is removed by this washing treatment.
-TG-DTA (Seiko Instruments TG / DTA6300 type) is used to measure the weight loss of each particle obtained under air reflux conditions from room temperature to 950 ° C.
The weight reduction from 200 to 600 ° C. is defined as a modified component that has been bonded to the particle surface, and the weight fraction of the component amount relative to the total amount of particles is defined as the surface modified amount.
The specifications of each example , reference example and comparative example, and the results of the surface modification amount are shown in Table 1.

As in Reference Example 1 and Comparative Examples 1-1 and 1-2, when the Example with the same number is compared with the Comparative Example, the surface modification amount of the Example is greatly improved in any case. It can be seen that when the concentration of the metal compound (A) is low, the amount of modification decreases particularly when the molecular weight of the compound (C) increases. Moreover, even if the density | concentration of a metal compound (A) is the range of this invention, when a metal compound (B) does not exist, it turns out that it is hardly modified.

  The present invention has been described in detail above with reference to specific examples. However, the present invention is not limited to the above contents, and various modifications and changes can be made without departing from the scope of the present invention.

Claims (10)

A first step of producing a particulate metal oxide solution containing a particulate metal oxide ( A) having a hydroxyl group on the surface at a concentration of 30 to 70 wt%;
A second step of adding a metal compound (B) having one or more alkoxy groups to the particulate metal oxide solution to react with at least part of the surface hydroxyl groups of the particulate metal oxide (A). When,
A third step of mixing the metal compound (B) and the compound (C) having chemical binding ability with the particulate metal oxide solution, and reacting with at least a part of the metal compound (B);
The equipped,
The metal compound (B) has in addition to the epoxy groups of the one or more alkoxy groups, the compound (C), you characterized polycarbonate resin der Rukoto having terminal hydroxyl groups, particulate metal A method for producing an oxide derivative. A first step of producing a particulate metal oxide solution containing a particulate metal oxide ( A) having a hydroxyl group on the surface at a concentration of 30 to 70 wt%;
A second step of adding a metal compound (B) having one or more alkoxy groups to the particulate metal oxide solution to react with at least part of the surface hydroxyl groups of the particulate metal oxide (A). When,
A third step of mixing the metal compound (B) and the compound (C) having chemical binding ability with the particulate metal oxide solution, and reacting with at least a part of the metal compound (B);
The equipped,
The metal compound (B) has in addition to the amino group of said one or more alkoxy groups, the compound (C), you characterized polycarbonate resin der Rukoto having an epoxy group at the terminal, the particulate A method for producing a metal oxide derivative. In the second step, the metal compound (B) is added to the particulate metal oxide solution at a temperature lower by 5 to 10 ° C. than the boiling point of the solvent constituting the particulate metal oxide solution. The method for producing a particulate metal oxide derivative according to claim 1 or 2 , characterized in that In said 3rd process, mixing to the said particulate metal oxide solution of said compound (C) is performed at a temperature range of 70-130 degreeC, It is any one of Claims 1-3 characterized by the above-mentioned. The manufacturing method of the particulate metal oxide derivative of description. In the third step, the concentration of the reaction product of the particulate metal oxide (A) and the metal compound (B) in the particulate metal oxide solution is in the range of 30 to 70 wt%. The manufacturing method of the particulate metal oxide derivative as described in any one of Claims 1-4 characterized by the above-mentioned. In the third step, after the compound (C) which is a solution dissolved in a predetermined solvent, characterized in that so as to mix with respect to the particulate metal oxide solution to Claim 5 The manufacturing method of the particulate metal oxide derivative of description. Extracting the reaction product of the particulate metal oxide (A) and the metal compound (B) from the particulate metal oxide solution between the second step and the third step, Comprising the fourth step of re-dissolving the reactant in a solvent different from the solvent constituting the particulate metal oxide solution to produce a reactant solution;
4. The method according to claim 1, wherein, in the third step, the compound (C) is mixed with the reactant solution instead of the particulate metal oxide solution . 5. A method for producing the particulate metal oxide derivative according to 1. The particulate metal oxide derivative according to claim 7 , wherein in the third step, the concentration of the reactant in the reactant solution is in the range of 30 to 70 wt%. Method. The method for producing a particulate metal oxide derivative according to any one of claims 1 to 8 , wherein the particulate metal oxide (A) is at least one of silica and alumina. The method for producing a particulate metal oxide derivative according to any one of claims 1 to 9 , wherein the solvent constituting the particulate metal oxide solution is water.