JP2010150321A - Polysiloxane composition and method for preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polysiloxane composition containing fine particles of metal oxide having an organosilicon group on a surface thereof, and a method for preparing the same. <P>SOLUTION: The polysiloxane composition comprises a polysiloxane represented by average composition formula (A): R<SP>1</SP><SB>m</SB>X<SB>n</SB>SiO<SB>[(4-m-n)/2]</SB>and fine particles of metal oxide having an organosilicon group of general formula (B): R<SP>1</SP><SB>p</SB>X<SB>q</SB>SiO<SB>[(4-p-q)/2]</SB>fixed on a surface thereof by chemical bond. The method for preparing the polysiloxane composition is characterized in that the polysiloxane and fine particles of the metal oxide are simultaneously formed by reacting fine particles of metal oxide and an organosilicon compound having a silicon atom bonded hydrolyzable group or a silanol group, and having a substituted or unsubstituted monovalent hydrocarbon group under conditions of a temperature of ≥200°C in the presence of water. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polysiloxane composition containing metal oxide fine particles having an organosilicon group on the surface.

  Ultrafine particles, generally called nanoparticles, have different surface properties than conventional fine powders due to their large surface energy, such as changes in optical properties due to quantum size effects, lowering of melting point, high catalytic properties, high magnetic properties, etc. Therefore, application in various fields such as electronic materials, optical materials, catalyst materials, luminescent materials, and pharmaceuticals is expected. However, since these ultrafine particles are very easily aggregated, the surface is generally modified with an organic group. The method for producing the surface-modified nanoparticles is described in JP-A No. 2007-51188, JP-A No. 2006-282503, JP-A No. 11-92687, and JP-A No. 10-183207. Various methods are known.

  In order to express the useful properties of nanoparticles in a polymer material, it is necessary to disperse the nanoparticles in the polymer material without agglomeration, and various methods have been proposed for this purpose. For example, Journal of Powder Engineering, 40 (7), 487-96 (2003) proposes a method of dispersing surface-modified silica nanoparticles in a polymer by a twin screw extruder, and Macromol. Mater. Eng., 2003, 288, 717-723 reports a method of simultaneously producing nanoparticles and dispersing them in a polymer by a sol-gel reaction between a polymer having a hydrolyzable group and a nanoparticle precursor. However, these methods have problems that it is necessary to appropriately modify the particle surface in advance, and that the synthesis of the hydrolysis-reactive polymer is complicated.

  On the other hand, Japanese Patent Application Laid-Open No. 9-302257 describes composite fine particles that are combined with a polymer by hydrolysis / condensation reaction, and Japanese Patent Application Laid-Open No. 2002-210356 discloses high-pressure carbon dioxide. Composite fine particles that have been used and complexed with polymers are described. However, these techniques also have problems such as that it takes a long time to complete both processes of polymer synthesis and fine particle generation, and it is difficult to control the uniformity of the polymer layer to be coated. Further, Japanese Patent Publication No. 6-47457 also proposes a method for producing organophilic silica having an organosilicon group on the surface by slowly treating silica fine particles with trialkoxysilane. However, there is a problem that an acid catalyst is required and the production time is long, and there is no description about the posilyloxane composition.

Thus, at present, no method has been reported for obtaining a nanoparticle-dispersed polymer composition that simultaneously and simply performs polymer synthesis reaction and nanoparticle dispersion in the produced polymer.
JP 2007-51188 A JP 2006-282503 A JP-A-11-92687 Japanese Patent Laid-Open No. 10-183207 Journal of Powder Engineering, 40 (7), 487-96 (2003) Macromol. Mater. Eng., 2003, 288, 717-723 JP-A-9-302257 JP 2002-210356 A Japanese Examined Patent Publication No. 6-47457

  The present invention has been made in view of the current state of the prior art, and an object thereof is to simply provide a composition in which metal oxide fine particles are well dispersed in a polymer.

  An object of the present invention is to provide a metal oxide fine particle and an organosilicon compound having a silicon atom bond hydrolyzable or silanol group and a substituted or unsubstituted monovalent hydrocarbon group at a temperature of 200 ° C. or higher in the presence of water. This is accomplished by reacting under temperature conditions.

The composition provided by the present invention has the following average composition formula (A):

^{_{R 1 m X n SiO [(}} 4-m-n) / 2] (A)

(Where
Each R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group;
Each X independently represents a silicon atom-bonded hydrolyzable group or silanol group;
m and n are numbers satisfying 0 <m, 0 ≦ n, and m + n <3, respectively.
And a polysiloxane represented by:
The following average composition formula (B):

R ¹ _p X _q SiO _{[(4-pq) / 2]} (B)

(Where
R ¹ and X are as described above,
p and q are numbers satisfying 0 <p, 0 ≦ q, and p + q <3, respectively)
An organic silicon group represented by the formula consists of metal oxide fine particles fixed on the surface by chemical bonds via oxygen atoms in the organosilicon group.

The organosilicon compound has the following general formula (C):

R ¹ _a SiX _(4-a) (C)

{Where,
R ¹ and X are as described above,
a is a reactive silane represented by 0 <a ≦ 2 is satisfied,}
And / or the following general formula (D):

R ¹ ₂ R ² SiO— (SiR ¹ R ² O) _s —SiR ¹ ₂ R ² (D)

(Where
R ¹ is as described above,
Each R ² independently represents a substituted or unsubstituted monovalent hydrocarbon group, or a silicon atom-bonded hydrolyzable group or silanol group;
s is a number satisfying 0 <s), a linear reactive organosiloxane oligomer represented by:
And / or the following general formula (E):

R ¹ _b X _c SiO _{[(4-b-c) / 2]} (E)

(Where
R ¹ and X are as described above,
b and c are each preferably a branched or reticulated siloxane represented by 0 <b <2, 0 <c <2, and b + c <2.

The hydrolyzable group or silanol group is represented by a halogen atom, a hydrogen atom, or a formula: —OR ³ (R ³ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 6 or less carbon atoms). A group represented by the formula: —OC (O) R ¹ (wherein R ¹ is as defined above), a formula: —O—N═CR ¹ ₂ (wherein R ¹ is as defined above). A group represented by the formula: —NR ⁴ —C (O) R ¹ (wherein R ¹ is as defined above, R ⁴ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group). And a group selected from the group consisting of groups represented by the formula: —ONH ₂ .

  The metal oxide is preferably a group IV to group XV metal oxide of the periodic table.

  The ratio of the content (weight) of the polysiloxane and the metal oxide fine particles is preferably in the range of 1:99 to 99: 1.

  In the polysiloxane composition obtained by the present invention, since the metal oxide fine particles are well dispersed in the polysiloxane, the polysiloxane composition can well exhibit the characteristics derived from the fine particles. In particular, in addition to the excellent light transmittance, electrical insulation, light stability, heat stability, and cold resistance of polysiloxane, the characteristics of the particles can be expressed.

  The method for producing the polysiloxane composition of the present invention does not use a large amount of an organic solvent, and therefore has a low environmental burden and is safe. Moreover, since it can implement with a simple apparatus, manufacturing cost can be suppressed. In addition, polysiloxane can be synthesized without using an acid catalyst or a base catalyst.

  In the method for producing a polysiloxane composition of the present invention, metal oxide fine particles and polysiloxane having an affinity for polysiloxane can be produced at a time by simultaneously performing a polymer synthesis reaction and a fine particle surface modification reaction. Moreover, fine particles can be well dispersed in the polysiloxane.

The polysiloxane composition obtained by the present invention is:
(A) The following average composition formula (A):

^{_{R 1 m X n SiO [(}} 4-m-n) / 2] (A)

(Where
R ¹ each independently represents a substituted or unsubstituted monovalent hydrocarbon group; X each independently represents a silicon atom-bonded hydrolyzable group or silanol group; 0 <m, 0 <n, and a number satisfying m + n <3), and
(B) The following average composition formula (B):

R ¹ _p X _q SiO _{[(4-pq) / 2]} (B)

(Where
R ¹ and X are as defined above; p and q are each a number satisfying 0 <p, 0 ≦ q, and m + p + q <3). It essentially contains metal oxide fine particles immobilized on the surface by chemical bonds via oxygen atoms in the silicon group.

In the average composition formula (A) representing the (a) polysiloxane, the monovalent hydrocarbon group for R ¹ is typically substituted or unsubstituted, having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms. 10, more preferably a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, 6 to 20 carbon atoms, more preferably a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or 2 to 20 carbon atoms Is a monovalent unsaturated aliphatic hydrocarbon group.

  Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Examples include linear or branched alkyl groups such as a pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group, and cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. It is done.

  Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include aryl groups such as a phenyl group, a tolyl group, a xylyl group, and a mesityl group. A phenyl group is preferred. In addition, in this specification, the aromatic hydrocarbon group includes a group in which an aromatic hydrocarbon and an aliphatic saturated hydrocarbon are combined in addition to a group consisting of only an aromatic hydrocarbon. Examples of the group in which an aromatic hydrocarbon and a saturated hydrocarbon are combined include an aralkyl group such as a benzyl group or a phenethyl group.

  Examples of the monovalent unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms include a vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl, 2-butenyl group, pentenyl group, Linear or branched alkenyl group such as hexenyl group, cycloalkenyl group such as cyclopentenyl group and cyclohexenyl group, and cycloalkenylalkyl such as cyclopentenylethyl group, cyclohexenylethyl group and cyclohexenylpropyl group Groups. A vinyl group and a cyclohexenylethyl group are preferred.

  The hydrogen atom on the monovalent hydrocarbon group may be substituted with one or more substituents, and the substituents are selected from halogen atoms (fluorine atom, chlorine atom, bromine atom and iodine atom). .

X is independently a silicon atom-bonded hydrolyzable group or silanol group, and is not particularly limited, but specifically, a halogen atom, a hydrogen atom, a formula: —OR ³ (R ³ represents a hydrogen atom, or a group represented by a substituted or unsubstituted monovalent hydrocarbon group having 6 or less carbon atoms), a formula: —OC (O) R ¹ (R ¹ is as described above) A group represented by the formula: —O—N═CR ¹ ₂ (R ¹ is as defined above), a formula: —NR ⁴ —C (O) R ¹ (R ¹ is R ⁴ represents a hydrogen atom or a group represented by a substituted or unsubstituted monovalent hydrocarbon group, and a group selected from the group consisting of a group represented by the formula: —ONH ₂ It is preferable that

In addition, the monovalent hydrocarbon group for R ³ is not particularly limited, and specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl. And straight-chain or branched alkyl groups such as a tert-butyl group, and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. The hydrogen atom on these monovalent hydrocarbon groups may be substituted by one or more substituents, and the substituents are selected from halogen atoms (fluorine atom, chlorine atom, bromine atom and iodine atom). . Preferred R ³ is a hydrogen atom or a methyl group.

Further, the monovalent hydrocarbon group for R ⁴ is not particularly limited, but specific examples thereof include the same monovalent hydrocarbon groups as those for R ¹ . Preferred R ⁴ is a hydrogen atom or a methyl group.

  The (a) polysiloxane may be linear, branched or net-like. In the average composition formula (A) representing the (a) polysiloxane, m and n are numbers satisfying 0 <m, 0 <n, and m + n <3, respectively, and the value of m + n is 2 or more. If it is smaller than 2, it will be branched or net-like. Such (a) polysiloxane has, for example, a silicon-bonded alkoxy group and / or a hydroxyl group. Examples of the polysiloxane (a) include a linear diorganopolysiloxane having a silicon atom-bonded alkoxy group and / or a hydroxyl group at both ends of the molecular chain, a silicon atom-bonded alkoxy group at the molecular chain one end, and / or Linear diorganopolysiloxane having a hydroxyl group, alkoxy group having a silicon atom bond at the molecular chain end and pendant position and / or linear diorganopolysiloxane having a hydroxyl group, an alkoxy group having a silicon atom bond at the pendant position and / or Examples thereof include a cyclic diorganopolysiloxane having a hydroxyl group, a silicon atom-bonded alkoxy group and / or a silicone resin having a hydroxyl group.

The (b) metal oxide fine particles have the following average composition formula (B):

R ¹ _p X _q SiO _{[(4-pq) / 2]} (B)

(Where
R ¹ and X are as described above; p and q are numbers satisfying 0 <p, 0 ≦ q, and m + p + q <3, respectively)
The organic silicon group represented by the formula is not particularly limited as long as it is immobilized on the surface of the metal oxide fine particle by a chemical bond via an oxygen atom in the organosilicon group.

The metal constituting the metal oxide fine particles is not particularly limited, and any metal element can be used. Typically, the group IV element in the periodic table of elements and the right side thereof are used. Elements located on the line of the group XIII boron (B) -group XIV silicon (Si) -group XV arsenic (As) and from the line to the left to the lower side of the periodic table For example, Ti, Zr, etc. for Group IV elements, V, etc. for Group V elements, Cr, Mo, etc. for Group VI elements, Mn, etc. for Group VII elements, Group VIII to Fe, Co, Ni, Ru, Rh, Pd, Pt, etc. for Group X elements, Cu, etc. for Group XI elements, Zn, etc. for Group XII elements, Al, Ga, In, for Group XIII elements For example, Si, Ge, Sn, Pb, etc. for Group XIV elements, and Sb, Bi, etc. for Group XV elements. It is. Ti, Zr, Mn, Fe, Ni, Cu, Zn, Al, Si, Ge, and Sn are preferable, and Ti, Zr, Mn, Fe, Ni, Cu, Zn, Al, and Si are particularly preferable. These metal elements may be used alone or as a mixture of two or more. Therefore, examples of the metal oxide include oxides such as Ti, Zr, Fe, Ni, Cu, Zn, Al, Si, Ge, and Sn. For example, SiO ₂ , TiO ₂ , ZnO, SnO ₂ , Al ₂ O ₃ , AlOOH, MnO ₂ , NiO, Fe ₂ O ₃ , Fe ₃ O ₄ , ZrO ₂ , BaTiO ₃ , LiCoO ₂ , LiMn ₂ O ₄ , CuO, Cu ₂ O, and mixtures thereof may be mentioned . Al ₂ O ₃ , AlOOH, Cu ₂ O, CuO, SiO ₂ and ZrO ₂ are preferred.

  The shape of the fine particles is not particularly limited, and may be any shape such as a spherical shape, a spindle shape, a prismatic shape, a cylindrical shape, a plate shape, or a needle shape. A spherical one is preferred.

  The fine particles preferably have an average particle size of 1 μm or less, particularly preferably nanoparticles. Nanoparticles generally mean particles having an average particle size of 200 nm or less, preferably 150 nm or less, more preferably 100 nm or less, still more preferably 50 nm or less, and even more preferably 30 nm or less. Especially preferably, it is 15 nm or less. The fine particles may be a mixture of fine particles having different particle sizes. The average particle diameter can be measured by a conventional measurement method in this field, for example, a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a scanning electron microscope (SEM), an electric field. The average value can be obtained by measuring the particle diameter with a radiation scanning electron microscope (FE-SEM) or the like.

  In the fine particles, the organosilicon group is fixed on the surface of the metal oxide fine particles by chemical bonds. Here, the chemical bond means a strong bond such as a covalent bond or an ionic bond, and does not include a bond based on simple physical adsorption or the like.

The organic silicon group represented by the general formula (B), but are not limited to, for _{example, -O- (Si (C 6 H} 5) 2 O) v -Si (C 6 _{H 5) 2 (OCH 3)} (v is a number of 1 or _{more), - O- (Si (C} 6 H 5) 2 O) w -Si (C 6 H 5) 2 (OH) (w 1 And the like).

  The ratio of the organosilicon group to the metal oxide is not particularly limited, but is preferably in the range of 1 to 200% by weight, more preferably 5 to 100% by weight. When the weight ratio of the organosilicon group is less than the lower limit of the above range, the dispersibility in the polysiloxane of the metal oxide fine particles in which the organosilicon group is immobilized by a chemical bond may be deteriorated. On the other hand, when the upper limit of the above range is exceeded, there is a possibility that useful properties such as heat resistance are hardly imparted to the polysiloxane by the metal oxide fine particles.

  In the polysiloxane composition of the present invention, the content (weight) of the polysiloxane and the metal oxide fine particles in which the organosilicon group is fixed by a chemical bond is not particularly limited, but the ratio of both is 1:99 to An amount in the range of 99: 1 is preferred, and an amount in the range of 4:96 to 96: 4 is particularly preferred. When the content of the fine particles is less than 1% by weight, useful properties due to the fine particles are not sufficiently imparted. On the other hand, when the fine particles content exceeds 99% by weight, the polysiloxane has good light transmittance, electrical insulation, molding. There is a possibility that characteristics such as workability cannot be obtained.

  The polysiloxane composition of the present invention comprises a metal oxide fine particle aqueous dispersion and an organosilicon compound, or a metal oxide fine particle, an organosilicon compound, and water reacted at a temperature of 200 ° C. or higher, It can be produced by simultaneously forming polysiloxane and metal oxide fine particles having organosilicon groups immobilized on the surface by chemical bonds.

  The organic silicon compound is not particularly limited as long as it contains silicon, but organic compounds containing silicon atoms such as organosilanes and organosiloxane oligomers are preferable. These silicon atom-containing organic compounds may be used alone or in combination of two or more.

As organosilane, the following general formula (C):

R ¹ _a SiX _(4-a) (C)

(Where
R 1 ^and,, X, the are as; a is 0 <organosilane is preferably represented by a number) that satisfies a ≦ 2. One type of organosilane may be used alone, or two or more types may be mixed and used.

  Preferred organosilanes include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, methylvinyldimethoxysilane, methylphenyldimethoxysilane, methylchloropropyldimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane. Examples include methoxysilane and chloropropyltrimethoxysilane.

As the organosiloxane oligomer, the following general formula (D):

R ¹ ₂ R ² SiO— (SiR ¹ R ² O) _s —SiR ¹ ₂ R ² (D)

(Where
R ¹ is as defined above; each R ² independently represents a substituted or unsubstituted monovalent hydrocarbon group, or a silicon atom-bonded hydrolyzable group or silanol group, provided that in one molecule And at least one R ² in the molecule is the hydrolyzable group or silanol group, and at least one R ² in one molecule is a substituted or unsubstituted monovalent hydrocarbon group; is a linear organosiloxane oligomer represented by the following formula. Here, examples of the substituted or unsubstituted monovalent hydrocarbon group for R ² include the same groups as those described above for R ¹ . Examples of the silicon atom-bonded hydrolyzable group or silanol group for R ² include the same groups as those described above for X. One type of organosiloxane may be used alone, or two or more types may be mixed and used.

  Preferred organosiloxane oligomers include, for example, dimethylsiloxane oligomers having silicon atom-bonded methoxy groups at both molecular chain terminals and pendant positions, and dimethylsiloxane oligomers having hydroxyl groups at both molecular chain terminals and pendant positions.

Moreover, as another organosiloxane oligomer, the following general formula (E):

R ¹ _b X _c SiO _{[(4-b-c) / 2]} (E)

(Where
R ¹ and X are as described above,
b and c are each preferably a branched or reticulated siloxane represented by 0 <b <2, 0 <c <2, and b + c <2. One type of organosiloxane may be used alone, or two or more types may be mixed and used.

  In the method for producing a polysiloxane composition of the present invention, the metal oxide fine particles are in the form of an aqueous dispersion previously combined with water or without being combined with water, and the metal oxide fine particles and water are independent. Used in form.

  There is no limitation on the concentration of the metal oxide fine particles when the metal oxide fine particles are used in the form of an aqueous dispersion, but considering the production efficiency of the polysiloxane composition, it is preferably 0.1% by weight or more and 50% by weight or less. 1% by weight or more and 30% by weight or less is more preferable.

  The mixing ratio of the organic silicon compound and the metal oxide fine particles in water, or the metal oxide fine particles and water was fixed by chemical bonding of the polysiloxane and the organosilicon group in the polysiloxane composition. It is preferable to adjust the content (weight) ratio of the metal oxide fine particles to be in the range of 1:99 to 99: 1, and the mixing ratio to be in the range of 4:96 to 96: 4. Particularly preferred. When the content of the metal oxide fine particles is less than the lower limit of the above range, useful properties due to the fine particles are not sufficiently imparted, whereas when the upper limit of the above range is exceeded, the polysiloxane has good light transmittance, There is a possibility that characteristics such as electrical insulation and moldability cannot be obtained.

  In the method for producing a polysiloxane composition of the present invention, it is essential that water is present in the reaction system. As needed, alcohols such as methanol and ethanol, glycols such as ethylene glycol and propylene glycol, carboxylic acids such as formic acid and acetic acid, aldehydes such as formaldehyde and acetaldehyde, ketones such as acetone and methyl ethyl ketone, thiols such as methanethiol, methyl An amine such as amine or dimethylamine, ammonia, or a surfactant may be added to water. These addition amounts are preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight, and still more preferably 0.1 to 5% by weight, based on the total weight of water and metal oxide. When these are added to the aqueous dispersion of metal oxide fine particles, the dispersion stability and storage stability of the metal oxide fine particles can be improved.

  The preferable reaction temperature in the production method of the present invention is 250 ° C. or higher, and more preferably 300 ° C. or higher. Moreover, the preferable reaction pressure is 5 MPa or more, and 10 MPa or more is more preferable.

  In the production method of the present invention, the reaction time is not limited. An appropriate reaction time can be selected according to the shape and size of the apparatus to be implemented and according to the temperature increase rate of the reaction vessel. When the temperature rise rate of the reaction vessel is large, the reaction time may be short. On the other hand, when the temperature rise rate of the reaction vessel is small, it is generally preferable to lengthen the reaction time.

  An apparatus for carrying out the production method of the present invention is not particularly limited. For example, a general-purpose apparatus in the field such as a reaction tube made of a strong material such as SUS316 can be used. Specifically, an aqueous dispersion of metal oxide fine particles and an organosilicon compound, or metal oxide fine particles, an organosilicon compound, and water are enclosed in the reaction tube equipped with a thermometer, etc., and a salt bath or the like is heated. After the reaction tube is reacted at a temperature of 200 ° C. or higher for a predetermined time by means, the reaction tube is cooled and the product in the reaction tube is recovered.

  In the production method of the present invention, water is basically used and a large amount of organic solvent is not used. Therefore, the influence on the environment is small and safe. And since the complicated manufacturing apparatus is not required, the polysiloxane composition of this invention can be manufactured in large quantities at low cost.

  The polysiloxane composition of the present invention can be used alone or in combination with other components in the fields of paints, pigments, cosmetics, catalysts, glasses, pharmaceuticals and the like. For example, the polysiloxane composition of the present invention containing fine particles made of silica can be used as a heat resistant coating material.

  The polysiloxane composition of the present invention and the production method thereof will be described in detail with reference to examples and comparative examples. The identification of the polysiloxane in the polysiloxane composition, the identification of the metal oxide fine particles having the organosilicon group immobilized on the surface, and the observation of the dispersion state of the metal oxide fine particles in the composition are as follows. I went.

[Chemical structure of polysiloxane]
The chemical structure of the product polysiloxane is an infrared absorption spectrum (hereinafter abbreviated as IR) using a Fourier transform infrared spectrophotometer FT / IR-5300 manufactured by JASCO Corporation, and manufactured by Bruker BioSpin Corporation. The measurement was performed by ²⁹ Si-NMR spectrum measurement using a high-resolution nuclear magnetic resonance apparatus AC300P. Tetramethylsilane was used as a reference material for calculating a resonance frequency shift value in NMR measurement.

[Identification of metal oxide fine particles]
The chemical structure of the organosilicon group immobilized on the metal oxide fine particles was measured by the IR spectrum, and the weight ratio to the metal oxide fine particles was measured by thermogravimetry (hereinafter referred to as TGA) using TAS200-TG8110D manufactured by Rigaku Corporation. It was.

[Dispersion state of metal oxide fine particles]
The dispersion state of the metal oxide in which the organosilicon group in the metal oxide fine particle-containing polysiloxane composition as the product is immobilized is a transmission electron microscope (hereinafter abbreviated as TEM) H-8100 manufactured by Hitachi, Ltd. Was observed.

[Example 1]
0.84 ml of an aqueous dispersion of silica particles having an average particle diameter of 15 nm (manufactured by Fuso Chemical Industry Co., Ltd., PL-1; silica particle concentration: 12% by weight) in a reaction tube made of SUS316 having an inner diameter of 10.4 mm and an inner volume of 10 cm ^3. And 1.21 ml of phenyltrimethoxysilane were charged and the cap was closed. This mixture was put into a salt bath heated to 300 ° C., heated for 10 minutes, quenched in a water bath, and opened. The product was a phase separated mixture of a white solid and a colorless transparent liquid. The separated solid was dried under reduced pressure at 100 ° C. to obtain a white solid product with an isolated yield of 92%. By extracting this solid with toluene, polysiloxane as a soluble component and silica having an organosilicon group as an insoluble component immobilized on the surface were separated.

From the spectral data summarized below, this soluble polysiloxane has an average composition formula:
(C ₆ H ₅ ) _1.0 (R ⁵ O) _0.16 SiO _1.42
It was confirmed that the polysiloxane was (wherein R ⁵ represents CH ₃ and H).
IR (cm ⁻¹ ): 3,630, 3,480, 3,075, 3,020, 2,955, 2,865, 1,595, 1,436, 1,160, 925, 744, 700
²⁹ Si NMR: -70.0, -78.5

From the IR spectrum of silica having an organosilicon group immobilized on the surface, the following absorption peak is observed, and the structure of the organosilicon group has an average composition formula:
(C ₆ H ₅ ) _1.0 (R ⁵ O) _0.16 SiO _1.42
(Wherein R ⁵ represents CH ₃ and H).
IR (cm ^-1 ): 3,480, 1,638, 1,436, 1,160, 964, 805, 744, 700
Further, from the result of TGA, the ratio of the organosilicon group to the silica was 25% by weight.

  From the result of TEM measurement of the product, it was found that substantially spherical silica fine particles were dispersed in polysiloxane without aggregation. The average particle diameter of the fine particles was 15 nm, and it was confirmed that the size in the silica dispersion before the reaction was maintained.

  Furthermore, the weight ratio of the silica fine particles in which the organosilicon group in the metal oxide fine particle-containing polysiloxane composition was immobilized on the surface by chemical bonding and the polysiloxane was 14:86.

[Example 2]
Except for using 0.87 ml of an aqueous dispersion of silica particles having an average particle diameter of 10-20 nm (manufactured by Nissan Chemical Industries, Ltd., Snowtex O; silica particle concentration: 20% by weight) as an aqueous dispersion of metal oxide. The reaction was carried out in the same manner as in Example 1 to obtain a phase separated mixture of a white solid and a colorless transparent liquid as a product. The separated solid was dried under reduced pressure at 100 ° C. to obtain a white solid product with an isolated yield of 94%. By extracting this solid with toluene, polysiloxane as a soluble component and silica having an organosilicon group as an insoluble component immobilized on the surface were separated.

From the spectral data summarized below, this soluble polysiloxane has an average composition formula:
(C ₆ H ₅ ) _1.0 (R ⁵ O) _0.12 SiO _1.44
It was confirmed that the polysiloxane was (wherein R ⁵ represents CH ₃ and H).
IR (cm ⁻¹ ): 3,628, 3,480, 3,076, 3,022, 2,950, 2,868, 1,595, 1,436, 1,155, 930, 744, 700
²⁹ Si NMR: -69.0, -78.0

From the IR spectrum of silica having an organosilicon group immobilized on the surface, the following absorption peak is observed, and the structure of the organosilicon group has an average composition formula:
(C ₆ H ₅ ) _1.0 (R ⁵ O) _0.12 SiO _1.44
(Wherein R ⁵ represents CH ₃ and H).
IR (cm ⁻¹ ): 3,480, 1,637, 1,436, 1,155, 960, 805, 744, 700
Further, from the result of TGA, the ratio of the organosilicon group to the silica was 22% by weight.

  As a result of TEM measurement of the product, it was found that substantially spherical silica fine particles were dispersed in polysiloxane without aggregation. The average particle diameter of the fine particles was 10-20 nm, and it was confirmed that the size in the silica dispersion before the reaction was maintained.

  Furthermore, the weight ratio of the silica fine particles in which the organosilicon groups in the metal oxide fine particle-containing polysiloxane composition were immobilized on the surface by chemical bonding and the polysiloxane was 23:77.

[Example 3]
The reaction is performed in the same manner as in Example 1 except that 2 ml of PL-1 and 0.042 ml of phenyltrimethoxysilane are used as an aqueous dispersion of metal oxide to produce a phase separated mixture of a white solid and a colorless transparent liquid. Obtained as a thing. The separated solid was dried under reduced pressure at 100 ° C. to obtain a white solid product with an isolated yield of 94%. By extracting this solid with toluene, polysiloxane as a soluble component and silica having an organosilicon group as an insoluble component immobilized on the surface were separated.

From the spectral data summarized below, this soluble polysiloxane has an average composition formula:
(C ₆ H ₅ ) _1.0 (R ⁵ O) _0.10 SiO _1.45
It was confirmed that the polysiloxane was (wherein R ⁵ represents CH ₃ and H).
IR (cm ^-1 ): 3,630, 3,480, 3,076, 3,020, 2,955, 2,867, 1,595, 1,436, 1,158, 925, 744, 700
²⁹ Si NMR: -69.5, -78.0

From the IR spectrum of silica having an organosilicon group immobilized on the surface, the following absorption peak is observed, and the structure of the organosilicon group has an average composition formula:
(C ₆ H ₅ ) _1.0 (R ⁵ O) _0.10 SiO _1.45
(Wherein R ⁵ represents CH ₃ and H).
IR (cm ^-1): 3,480,1,638,1,436,1,158,964,805,744,700
Further, from the result of TGA, the ratio of the organosilicon group to the silica was 6% by weight.

  From the result of TEM measurement of the product, it was found that substantially spherical silica fine particles were dispersed in polysiloxane without aggregation. The average particle diameter of the fine particles was 15 nm, and it was confirmed that the size in the silica dispersion before the reaction was maintained.

  Further, the weight ratio of the silica fine particles in which the organosilicon groups in the metal oxide fine particle-containing polysiloxane composition were immobilized on the surface by chemical bonding and the polysiloxane was 96: 4.

[Example 4]
Implemented except that 0.26 g of silica fine particles with an average particle size of 25 nm and 1.89 ml of water were used instead of 0.84 ml of an aqueous dispersion of silica particles with an average particle size of 15 nm and the amount of phenyltrimethoxysilane was 0.38 ml. The reaction was carried out in the same manner as in Example 1 to obtain a phase separated mixture of a white solid and a colorless transparent liquid as a product. The separated solid was dried under reduced pressure at 100 ° C. to obtain a white solid product with an isolated yield of 92%. By extracting this solid with toluene, polysiloxane as a soluble component and silica having an organosilicon group as an insoluble component immobilized on the surface were separated.

From the spectral data summarized below, this soluble polysiloxane has an average composition formula:
(C ₆ H ₅ ) _1.0 (R ⁵ O) _0.16 SiO _1.42
It was confirmed that the polysiloxane was (wherein R ⁵ represents CH ₃ and H).
IR (cm ⁻¹ ): 3,630, 3,475, 3,076, 3,020, 2,955, 2,867, 1,595, 1,436, 1,158, 925, 744, 700
²⁹ Si NMR: -69.5, -78.5

From the IR spectrum of silica having an organosilicon group immobilized on the surface, the following absorption peak is observed, and the structure of the organosilicon group has an average composition formula:
(C ₆ H ₅ ) _1.0 (R ⁵ O) _0.16 SiO _1.42
(Wherein R ⁵ represents CH ₃ and H).
IR (cm ⁻¹ ): 3,475, 1,638, 1,436, 1,158, 964, 805, 744, 700
Further, from the result of TGA, the ratio of the organosilicon group to the silica was 9% by weight.

  From the TEM photograph of the product, it was found that the spherical silica fine particles were dispersed in the polysiloxane without aggregation. The average particle diameter of the fine particles was 25 nm, and it was confirmed that the size in the silica dispersion before the reaction was maintained.

  Furthermore, the weight ratio of the silica fine particles in which the organosilicon groups in the metal oxide fine particle-containing polysiloxane composition were immobilized on the surface by chemical bonding and the polysiloxane was 54:46.

[Comparative Example 1]
A reaction was carried out in the same manner as in Example 1 except that the temperature of the salt bath was changed to 175 ° C. to obtain a product. The product was a mixture of two kinds of transparent liquids having different specific gravities, and no silica-dispersed polysiloxane was produced.

[Comparative Example 2]
Instead of 0.84 ml of an aqueous dispersion of silica particles having an average particle diameter of 15 nm, a methyl isobutyl ketone dispersion of silica particles having an average particle diameter of 10-20 nm (manufactured by Nissan Chemical Industries, Ltd., MIBK-ST; silica particle concentration: 30 The reaction was carried out in the same manner as in Example 1 except that 0.58 ml (wt%) was used to obtain a product. The product was a phase separated mixture of a white solid and a colorless transparent liquid. The separated solid was dried at 100 ° C. under reduced pressure to obtain a white solid. This product was silica, and the polysiloxane was composed of fine particles of metal oxide having polysiloxane and organosilicon groups immobilized on the surface by chemical bonds. No composition was produced.

Claims (8)

Metal oxide fine particles, and an organosilicon compound having a silicon atom-bonded hydrolyzable group or silanol group and a substituted or unsubstituted monovalent hydrocarbon group, in the presence of water at a temperature of 200 ° C. or higher Characterized by reacting,
The following average composition formula (A):

^{_{R 1 m X n SiO [(}} 4-m-n) / 2] (A)

(Where
Each R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group;
Each X independently represents a silicon atom-bonded hydrolyzable group or silanol group;
m and n are numbers satisfying 0 <m, 0 ≦ n, and m + n <3, respectively.
And the following average composition formula (B):

^{_{R 1 p X q SiO [(}} 4-p-q) / 2] (B)

(Where
R ¹ and X are as described above,
p and q are numbers satisfying 0 <p, 0 ≦ q, and p + q <3, respectively)
The manufacturing method of the polysiloxane composition which consists of metal oxide fine particles by which the organic silicon group represented by these was fix | immobilized on the surface by the chemical bond through the oxygen atom in this organosilicon group. The organosilicon compound is represented by the following general formula (C):

R ¹ _a SiX _(4-a) (C)

(Where
Each R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group;
Each X independently represents a silicon atom-bonded hydrolyzable group or silanol group;
The production method according to claim 1, wherein a is an organic silane represented by 0 <a ≦ 2. The organosilicon compound has the following general formula (D):

R ¹ ₂ R ² SiO— (SiR ¹ R ² O) _s —SiR ¹ ₂ R ² (D)

(Where
Each R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group;
Each R ² independently represents a substituted or unsubstituted monovalent hydrocarbon group, or a silicon-bonded hydrolyzable group or silanol group, provided that at least one R ² in one molecule is silicon An atomic bond hydrolyzable group or silanol group,
The production method according to claim 1, wherein s is a linear organosiloxane oligomer represented by: 0 <s. The organosilicon compound has the following general formula (E):

R ¹ _b X _c SiO _{[(4-b-c) / 2]} (E)

(Where
Each R ¹ independently represents a substituted or unsubstituted monovalent hydrocarbon group;
Each X independently represents a silicon atom-bonded hydrolyzable group or silanol group;
The production method according to claim 1, wherein b and c are branched or reticulated siloxanes represented by 0 <b <2, 0 <c <2, and b + c <2, respectively. A silicon atom-bonded hydrolyzable group or silanol group is a halogen atom, a hydrogen atom, or a formula: —OR ³ (R ³ represents a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 6 or less carbon atoms) A group represented by the formula: —OC (O) R ¹ (R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group), a formula: —O—N═CR ¹ ₂ (R ¹ is a group represented by the formula: —NR ⁴ —C (O) R ¹ (wherein R ¹ is as defined above, R ⁴ is a hydrogen atom, or a substituted or unsubstituted monovalent group) The production method according to any one of claims 1 to 4, which is a group selected from the group consisting of a group represented by (a hydrocarbon group) and a group represented by the formula: -ONH _2. . The manufacturing method according to any one of claims 1 to 5, wherein the metal oxide is a group IV to group XV metal oxide of the periodic table. A polysiloxane composition obtained by the production method according to claim 1. The polysiloxane composition according to claim 7, wherein the ratio of the content (weight) of the polysiloxane and the metal oxide fine particles is 1:99 to 99: 1.