JP5083747B2 - Surface modification particles and surface modification method of fine inorganic particles - Google Patents

Description

  The present invention improves the dispersibility by preventing agglomeration of fine inorganic particles having an outer diameter ranging from about 10 nm to about 300 nm and improves the reactivity when dispersed in an organic resin or the like. The present invention relates to a method for surface modification of particles and fine inorganic particles.

  In recent years, as part of nanotechnology research, applied research on fine particles having a particle size of several hundred nanometers or less has been actively conducted. Although such fine particles can be produced as primary particles, they are easy to agglomerate because they are fine particles. If left as they are, they will agglomerate into micron-sized secondary particles. For this reason, in order to make it easy to disperse | distribute as a primary particle, it was desired to modify the surface of a primary particle. Moreover, in order to put the technology using such fine particles into practical use, it is required to organically modify the surface of the fine particles through a strong bond.

Therefore, in Patent Document 1, in order to meet such a demand by modifying the surface of nano-sized fine particles with organic compounds such as hydrocarbons, fine particles using high-temperature and high-pressure water, particularly water in a supercritical state as a reaction field. Discloses a technique for strongly bonding hydrocarbons or the like to the surface of the steel. Patent Document 2 discloses an invention of an ink jet recording material in which the primary average particle diameter of silica fine particles of the ink receiving layer in the ink jet recording material is 10 nm to 50 nm and contains at least gelatin as a hydrophilic binder. ing.
JP 2005-194148 A JP 2002-264482 A

  However, the technique described in Patent Document 1 requires a very high temperature and high pressure in order to strongly bond hydrocarbons or the like to the surface of fine particles using water in a supercritical state as a reaction field, and is practically used as a surface modification method for fine particles. There was a problem that it was not right. Further, in the technique described in Patent Document 2, ultrasonic, high-pressure homogenizer, counter-impact collision type jet pulverization is performed until the vapor-phase-process silica, which is agglomerated into secondary particles, becomes secondary particles of about 100 nm to 500 nm. It is to be pulverized and dispersed by a machine or the like and not to be easily dispersed as primary particles.

  Therefore, the present invention improves the dispersibility and prevents the aggregation of the fine inorganic particles by allowing the surface modifier to freely enter between the primary particles of the fine inorganic particles aggregated into the secondary particles. An object of the present invention is to provide a surface modification particle and a surface modification method of fine inorganic particles that can be improved.

The surface-modified particles according to the invention of claim 1 are surface-modified particles obtained by surface-modifying fine inorganic particles having a particle diameter in the range of 20 nm to 130 nm, and an organic solvent and a surface modifier are added to the fine inorganic particles. A mixture is prepared, and the surface modifier is reacted and added to the surface of the fine inorganic particles as a supercritical state of the organic solvent by applying high temperature and high pressure to the mixture.
The surface modifier is an isocyanate compound. Here, the “isocyanate compound” means a compound having one or more isocyanate groups (—N═C═O).
The surface modified particles are compounds having an alkyl group. Here, the “alkyl group” means an aliphatic hydrocarbon group including a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
And as the surface modifier, a compound having an aryl group. Here, the “aryl group” means an aromatic hydrocarbon group including a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a duryl group, an anisyl group, and a naphthyl group.
Further, as the surface modifier, a compound having a UV functional group. Here, the “UV functional group” means a functional group that reacts with ultraviolet rays (UV) including a vinyl group, a styryl group, and an acrylic group.
In addition, the surface modified particles are hollow particles made of a silica shell having an outer diameter of 20 nm to 130 nm.

  The surface-modified particles according to the invention of claim 2 are those having the structure of claim 1 in which a high-temperature and high-pressure is applied to the mixture using an autoclave to bring the organic solvent into a supercritical state.

  The surface-modified particles according to the invention of claim 3 are the structures of claim 1 or claim 2, wherein the organic solvent is n-hexane.

The surface modification method for fine inorganic particles according to the invention of claim 4 is a method for surface modification of fine inorganic particles having a particle diameter in the range of 20 nm to 130 nm , wherein an organic solvent and a surface modifier are added to the fine inorganic particles. In addition, the method includes a step of preparing a mixture and a step of reacting and adding the surface modifier to the surface of the fine inorganic particles as a supercritical state of the organic solvent by applying high temperature and high pressure to the mixture.
The surface modifier is an isocyanate compound. Here, the “isocyanate compound” means a compound having one or more isocyanate groups (—N═C═O).
The surface modified particles are compounds having an alkyl group. Here, the “alkyl group” means an aliphatic hydrocarbon group including a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
And as the surface modifier, a compound having an aryl group. Here, the “aryl group” means an aromatic hydrocarbon group including a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a duryl group, an anisyl group, and a naphthyl group.
Further, as the surface modifier, a compound having a UV functional group. Here, the “UV functional group” means a functional group that reacts with ultraviolet rays (UV) including a vinyl group, a styryl group, and an acrylic group.
In addition, the surface modified particles are hollow particles made of a silica shell having an outer diameter of 20 nm to 130 nm.

In the method for modifying the surface of fine inorganic particles according to the invention of claim 5 , in the structure of claim 4 , the step of applying high temperature and pressure to the mixture is performed using an autoclave.

The surface modification method for fine inorganic particles according to the invention of claim 6 is the structure of claim 4 or claim 5 , wherein the organic solvent is n-hexane.

The surface-modified particles according to the invention of claim 1 are surface-modified particles obtained by surface-modifying fine inorganic particles having an outer diameter in the range of 20 nm to 130 nm, and an organic solvent and a surface modifier are added to the fine inorganic particles. Is added to the mixture, and a high temperature and high pressure is applied to the mixture to form a supercritical state of the organic solvent, and a surface modifier is reacted and added to the surface of the fine inorganic particles.
Here, as the “organic solvent”, aliphatic alcohols such as methanol, ethanol and propanol, aliphatic hydrocarbons such as n-hexane, aromatic hydrocarbons such as xylene, and the like can be used. In addition, as the “surface modifier”, an isocyanate compound, an amine compound, a vinyl compound, an epoxy compound, a methacryloxy compound, an acrylic compound, an imide compound, a compound having an alkyl group, a compound having an aryl group, Etc. can be used.
Fine inorganic particles having an outer diameter in the range of 20 nm to 130 nm are easy to aggregate in a dispersion medium to form secondary particles. In order to prevent aggregation and disperse as primary particles, use a disperser. Although it is necessary to vigorously disperse by vigorous stirring, it is often difficult to disperse completely.
The surface modified particles according to the present invention are obtained by applying high temperature and pressure to a mixture obtained by adding an organic solvent and a surface modifier to fine inorganic particles having an outer diameter in the range of 20 nm to 130 nm. As a result, the organic solvent freely enters the secondary particles together with the surface modifier, and the surface modifier reacts and adds to the entire surface of the primary particles, so that the aggregation is solved and the surface of the fine inorganic particles is the surface. The surface-modified particles covered with the modifier are easy to disperse as primary particles, and when dispersed in an organic resin or the like, the active group of the surface modifier reacts with the active group of the organic resin or the like and becomes strong. Form a dispersed state.
In this way, by allowing the surface modifier to freely enter between the primary particles of the fine inorganic particles agglomerated into the secondary particles, the fine inorganic particles are prevented from agglomerating and dispersibility is improved. When dispersed, the surface modified particles can improve the reactivity.
In the surface modified particles used in the present invention, the surface modifier can be an isocyanate compound. As described above, the term “isocyanate compound” means an organic compound having at least one isocyanate group (—N═C═O). Specific examples include three isocyanate groups in an alkyl group. There are bonded triisocyanate compounds, triethoxypropyl isocyanate silane (TEIS) and the like .
As described above, as the surface modifier, isocyanate compounds, amine compounds, vinyl compounds, epoxy compounds, methacryloxy compounds, acrylic compounds, imide compounds, compounds having an alkyl group, compounds having an aryl group, etc. Among these compounds, isocyanate compounds are easily available and have good reactivity, and are excellent in dispersibility and reactivity of the resulting surface-modified particles.
Such an isocyanate-based surface modifier is added via hydroxyl groups (—OH) present on the surface of the fine inorganic particles, and the entire surface of the fine inorganic particles is coated with the isocyanate-based surface modifier, thereby re-applying. Aggregation can be prevented, dispersibility is improved, and even when mixed in an organic resin, the active group of the organic resin and the isocyanate group react to form a strong bond between the organic resin and the fine inorganic particles. Is obtained.

Further, the surface-modified particles used in the present invention can be compounds in which the surface modifier has an alkyl group. Here, as described above, the “alkyl group” means an aliphatic hydrocarbon group including a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
Thus, by using a compound having an alkyl group as the surface modifier, the compound having an alkyl group is easily available and has good reactivity, and the surface modified particles obtained have excellent dispersibility and reactivity. Have advantages.
By adding such a surface modifier having an alkyl group via a hydroxyl group (—OH) present on the surface of the fine inorganic particle, and coating the entire surface of the fine inorganic particle with a surface modifier having an alkyl group , Re-aggregation can be prevented, dispersibility is improved, and even when mixed in an organic resin, the organic resin and the alkyl group are compatible with each other, so that fine inorganic particles are uniformly dispersed in the organic resin. To do.

And the surface modification particle | grains used by this invention can be made into the compound in which a surface modifier has an aryl group. Here, as described above, the “aryl group” means an aromatic hydrocarbon group including a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a duryl group, an anisyl group, and a naphthyl group. .
Thus, by using a compound having an aryl group as a surface modifier, the compound having an aryl group is easily available and has good reactivity, and the surface modified particles obtained have excellent dispersibility and reactivity. Have advantages.
By adding such a surface modifier having an aryl group via a hydroxyl group (—OH) present on the surface of the fine inorganic particle, the entire surface of the fine inorganic particle is coated with a surface modifier having an aryl group. Re-aggregation can be prevented and dispersibility is improved, and also when mixed in an organic resin, especially an aromatic organic resin, the aromatic organic resin and the aryl group are compatible. The fine inorganic particles are uniformly dispersed in the aromatic organic resin. In addition, extremely good dispersibility can also be obtained when dispersed in an aromatic hydrocarbon solvent such as toluene or xylene.

Furthermore, the surface-modified particles used in the present invention can be a compound in which the surface modifier has a UV functional group. Here, as described above, the “UV functional group” means a functional group that reacts with ultraviolet rays (UV) including a vinyl group, a styryl group, and an acrylic group.
Such a surface modifier having a UV functional group is added via hydroxyl groups (—OH) present on the surface of the fine inorganic particles, and the entire surface of the fine inorganic particles is coated with a surface modifier having a UV functional group. Therefore, re-aggregation can be prevented, dispersibility is improved, and even when mixed in an organic resin, the organic resin and the UV functional group are compatible with each other. Disperse uniformly.
Then, by coating the entire surface of the fine inorganic particles with a surface modifier having a UV functional group, a three-dimensional cross-linking reaction can be caused by ultraviolet (UV) irradiation, and a three-dimensional cross-linked product can be obtained.

In addition, the surface-modified particles of the present invention are hollow particles composed of silica shells in which fine inorganic particles have an outer diameter in the range of 20 nm to 130 nm.
In recent years, research and development on nano hollow particles made of silica shells has been actively carried out, and the manufacturing method has been almost established, but nano hollow particles made of silica shells having an outer diameter of 20 nm to 130 nm are also Like actual fine particles, they tend to agglomerate and are difficult to disperse, and have the problem that it is difficult to make use of the characteristics of nano hollow particles.
Therefore, as with solid fine particles, the organic solvent is brought into the supercritical state by applying high temperature and high pressure to a mixture of the organic hollow particles made of silica shell and the surface modifier added to the nano hollow particles made of silica shell. Surface modified particles that freely enter into the secondary particles together with the modifier, and the surface modifier is reacted and added to the entire surface of the primary particles, so that the aggregation is released and the surface of the fine inorganic particles is covered with the surface modifier. However, when dispersed in an organic resin or the like, the active group of the surface modifier reacts with the active group of the organic resin or the like to form a strong dispersion state.

The surface-modified particles according to the invention of claim 2 are brought into a supercritical state of an organic solvent by applying high temperature and high pressure to the mixture using an autoclave.
In order to allow the organic solvent to enter the secondary particles freely together with the surface modifier with the organic solvent in a supercritical state, it is necessary to apply high temperature and pressure to the mixture, but by using an autoclave, the temperature can be safely and freely increased. A high pressure can be applied, and a surface modifier can be reacted and added to the entire surface of the primary particles.
In this way, by allowing the surface modifier to freely enter between the primary particles of the fine inorganic particles agglomerated into the secondary particles, the fine inorganic particles are prevented from agglomerating and dispersibility is improved. When dispersed, the surface modified particles can improve the reactivity.

In the surface-modified particles according to the invention of claim 3, the organic solvent is n-hexane. As described above, as the organic solvent, aliphatic alcohols such as methanol, ethanol, and propanol, aliphatic hydrocarbons such as n-hexane, aromatic hydrocarbons such as xylene, and the like can be used. -Hexane has the lowest critical temperature and critical pressure and can be most easily brought to the supercritical state.
In this way, the surface modifier can be freely allowed to enter between the primary particles of the fine inorganic particles aggregated into the secondary particles with the organic solvent in the supercritical state most easily, thereby preventing the fine inorganic particles from aggregating. In addition to improving dispersibility, the surface modified particles can improve the reactivity when dispersed in an organic resin or the like.

The surface modification method for fine inorganic particles according to the invention of claim 4 is a method for surface modification of fine inorganic particles having a particle diameter in the range of 20 nm to 130 nm , wherein the fine inorganic particles are surface-modified with an organic solvent. A step of preparing a mixture by adding an agent, and a step of reacting and adding a surface modifier to the surface of the fine inorganic particles as a supercritical state of an organic solvent by applying high temperature and high pressure to the mixture.
The method for surface modification of fine inorganic particles according to the present invention includes adding organic solvent and a surface modifier to a fine inorganic particle having a particle diameter in the range of 20 nm to 130 nm and applying high temperature and high pressure to the mixture. By setting the supercritical state of the organic solvent, the organic solvent freely enters the secondary particles together with the surface modifier, and the surface modifier reacts and adds to the entire surface of the primary particles, so that the aggregation is solved and fine inorganic particles are dissolved. The surface-modified particles whose surface is covered with the surface modifier are easily dispersed as primary particles, and when dispersed in an organic resin or the like, the active group of the surface modifier reacts with the active group of the organic resin or the like. Thus, a strong dispersion state is formed.
In this way, by allowing the surface modifier to freely enter between the primary particles of the fine inorganic particles agglomerated into the secondary particles, the fine inorganic particles are prevented from agglomerating and dispersibility is improved. When dispersed, the surface modification method for fine inorganic particles can improve the reactivity.

In the surface modification method for fine inorganic particles according to the present invention, the surface modifier can be an isocyanate compound.
As described above, as the surface modifier, isocyanate compounds, amine compounds, vinyl compounds, epoxy compounds, methacryloxy compounds, acrylic compounds, imide compounds, compounds having an alkyl group, compounds having an aryl group, Among these, the isocyanate compounds are easily available, have good reactivity, and are excellent in dispersibility and reactivity of the resulting surface-modified particles.
Such an isocyanate-based surface modifier is added via hydroxyl groups (—OH) present on the surface of the fine inorganic particles, and the entire surface of the fine inorganic particles is coated with the isocyanate-based surface modifier, thereby re-applying. Aggregation can be prevented, dispersibility is improved, and even when mixed in an organic resin, the active group of the organic resin and the isocyanate group react to form a strong bond between the organic resin and the fine inorganic particles. Is obtained.

In the surface modification method for fine inorganic particles according to the present invention, the surface modifier can be a compound having an alkyl group.
Thus, by using a compound having an alkyl group as the surface modifier, the compound having an alkyl group is easily available and has good reactivity, and the surface modified particles obtained have excellent dispersibility and reactivity. Have advantages.
By adding such a surface modifier having an alkyl group via a hydroxyl group (—OH) present on the surface of the fine inorganic particle, and coating the entire surface of the fine inorganic particle with a surface modifier having an alkyl group , Re-aggregation can be prevented, dispersibility is improved, and even when mixed in an organic resin, the organic resin and the alkyl group are compatible with each other, so that fine inorganic particles are uniformly dispersed in the organic resin. To do.

In the surface modification method for fine inorganic particles according to the present invention, the surface modifier can be a compound having an aryl group.
Thus, by using a compound having an aryl group as a surface modifier, the compound having an aryl group is easily available and has good reactivity, and the surface modified particles obtained have excellent dispersibility and reactivity. Have advantages.
By adding such a surface modifier having an aryl group via a hydroxyl group (—OH) present on the surface of the fine inorganic particle, the entire surface of the fine inorganic particle is coated with a surface modifier having an aryl group. Re-aggregation can be prevented and dispersibility is improved, and also when mixed in an organic resin, especially an aromatic organic resin, the aromatic organic resin and the aryl group are compatible. The fine inorganic particles are uniformly dispersed in the aromatic organic resin. In addition, extremely good dispersibility can also be obtained when dispersed in an aromatic hydrocarbon solvent such as toluene or xylene.

In the surface modification method for fine inorganic particles according to the present invention, the surface modifier may be a compound having a UV functional group.
Such a surface modifier having a UV functional group is added via hydroxyl groups (—OH) present on the surface of the fine inorganic particles, and the entire surface of the fine inorganic particles is coated with a surface modifier having a UV functional group. Therefore, re-aggregation can be prevented, dispersibility is improved, and even when mixed in an organic resin, the organic resin and the UV functional group are compatible with each other. Disperse uniformly.
Then, by coating the entire surface of the fine inorganic particles with a surface modifier having a UV functional group, a three-dimensional cross-linking reaction can be caused by ultraviolet (UV) irradiation, and a three-dimensional cross-linked product can be obtained.

The surface modification method for fine inorganic particles according to the present invention is a hollow particle comprising a silica shell in which the fine inorganic particles have an outer diameter of 20 nm to 130 nm.
In recent years, research and development on nano hollow particles made of silica shells has been actively carried out, and the manufacturing method has been almost established, but nano hollow particles made of silica shells having an outer diameter of 20 nm to 130 nm are also Like actual fine particles, they tend to agglomerate and are difficult to disperse, and have the problem that it is difficult to make use of the characteristics of nano hollow particles.
Therefore, as with solid fine particles, the organic solvent is brought into the supercritical state by applying high temperature and high pressure to a mixture of the organic hollow particles made of silica shell and the surface modifier added to the nano hollow particles made of silica shell. Surface modified particles that freely enter into the secondary particles together with the modifier, and the surface modifier is reacted and added to the entire surface of the primary particles, so that the aggregation is released and the surface of the fine inorganic particles is covered with the surface modifier. However, when dispersed in an organic resin or the like, the active group of the surface modifier reacts with the active group of the organic resin or the like to form a strong dispersion state.

In the surface modification method for fine inorganic particles according to the invention of claim 5, the step of applying high temperature and high pressure to the mixture is performed using an autoclave.
In order to allow the organic solvent to enter the secondary particles together with the surface modifier in a supercritical state, it is necessary to apply a high temperature and high pressure to the mixture. By using an autoclave in this step, A high temperature and high pressure can be applied safely and freely, and a surface modifier can be reacted and added to the entire surface of the primary particles.
In this way, by allowing the surface modifier to freely enter between the primary particles of the fine inorganic particles agglomerated into the secondary particles, the fine inorganic particles are prevented from agglomerating and dispersibility is improved. When dispersed, the surface modification method for fine inorganic particles can improve the reactivity.

In the surface modification method for fine inorganic particles according to the invention of claim 6 , the organic solvent is n-hexane. As described above, as the organic solvent, aliphatic alcohols such as methanol, ethanol, and propanol, aliphatic hydrocarbons such as n-hexane, aromatic hydrocarbons such as xylene, and the like can be used. -Hexane (normal hexane, linear aliphatic hydrocarbon) has the lowest critical temperature and critical pressure, and can be most easily brought to the supercritical state.
In this way, the surface modifier can be freely allowed to enter between the primary particles of the fine inorganic particles aggregated into the secondary particles with the organic solvent in the supercritical state most easily, thereby preventing the fine inorganic particles from aggregating. In addition to improving the dispersibility, the surface modification method for fine inorganic particles can improve the reactivity when dispersed in an organic resin or the like.

  Embodiments of the present invention will be described below with reference to the drawings.

Embodiment 1
First, the surface modification particles and the surface modification method of fine inorganic particles according to the first embodiment of the present invention will be described with reference to FIGS. 1 to 3.

  FIG. 1 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 1 of the present invention. FIG. 2 is a schematic diagram showing Example 1 of the application method of the surface-modified particles according to the first embodiment of the present invention. FIG. 3 is a schematic diagram showing Example 2 of the application method of the surface-modified particles according to the first embodiment of the present invention.

  As shown in FIG. 1, in the surface-modified particles 3 according to the first embodiment, colloidal silica having an average particle diameter of 40 nm is used as the fine inorganic particles 1, and triethoxypropyl isocyanate silane ( Hereinafter, it is also referred to as “TEIS”). The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 1, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, by reacting TEIS2 as a surface modifier for 1 hour at a critical temperature (234.9 ° C.) and a critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent, n-hexane enters a supercritical state and freely enters between colloidal silica 1 aggregated as secondary particles, and all three ethoxy groups of TEIS2 undergo a condensation reaction with the hydroxyl groups on the surface of colloidal silica 1, thereby colloidal. Bonds to the surface of silica 1.

  As described above, the surface of colloidal silica 1 is covered with TEIS 2 as shown in FIG. 1 due to the reaction of innumerable hydroxyl groups on the surface of colloidal silica 1 with TEIS 2. The modified particles 3 are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which not only easily aggregate and disperse easily, but also the isocyanate group reacts with the active group of the organic resin to strengthen the organic resin. By forming a simple bond, the surface-modified particles 3 that are more easily uniformly dispersed in the organic resin can be obtained.

  A specific example of the application of the surface-modified particles 3 will be described with reference to FIG. As shown in FIG. 2, when the surface-modified particles 3 having an isocyanate group according to the first embodiment are dispersed in the organic resin 5, the active group (here, hydroxyl group) of the organic resin 5 reacts with the isocyanate group. Thus, a combined body 6 of the colloidal silica 1 having a urethane bond and the organic resin 5 is formed, and the surface modified particles 3 are uniformly and firmly dispersed in the organic resin 5.

  Next, Example 2 of a specific example of application of the surface modified particles 3 will be described with reference to FIG. As shown in FIG. 3, when the surface modified particles 3 according to the first embodiment having an isocyanate group are reacted with the inorganic fine particles 8, the hydroxyl groups on the surface of the inorganic fine particles 8 and the isocyanate groups react to form urethane bonds. A combined body of the colloidal silica 1 and the inorganic fine particles 8 is formed, and the composite 10 in which the surface of the colloidal silica 1 is uniformly and firmly covered with the inorganic fine particles 8 is formed.

  In this way, the surface-modified particles 3 according to the first embodiment are used as an organic solvent in colloidal silica 1 as fine inorganic particles having a particle size (average particle size of 40 nm) within a range of about 10 nm to about 300 nm. N-hexane and TEIS2 as a surface modifier were added to a supercritical state of n-hexane by applying high temperature and high pressure to allow n-hexane to freely enter the secondary particles together with TEIS2. The surface modification particles 3 in which the surface of the colloidal silica 1 is covered with the TEIS 2 can be easily dispersed as the primary particles by the reaction addition of the TEIS 2 over the entire surface of the primary particles, and dispersed in the organic resin 5 or the like. In this case, the isocyanate group which is an active group of TEIS2 reacts with an active group such as the organic resin 5 to form a strong dispersion state. .

Embodiment 2
Next, a surface modification method of the surface modified particles and fine inorganic particles according to the second embodiment of the present invention will be described with reference to FIGS. 4 and 5.

  FIG. 4 is a schematic diagram showing a surface-modified particle manufacturing process, a fine inorganic particle surface-modifying method, and an application example of the surface-modified particle according to Embodiment 2 of the present invention. FIG. 5 is a diagram showing the IR (infrared spectral absorption) spectrum of the surface-modified particles according to the second embodiment of the present invention compared with unmodified particles and coated particles.

  As shown in FIG. 4, in the surface modified particles 12 according to the second embodiment, hollow particles 11 made of silica shells having a particle size of about 50 nm to about 100 nm are used as fine inorganic particles, and the surface modifier is used as the surface modifier. Uses triethoxypropyl isocyanate silane (TEIS) 2 as in the first embodiment. Numerous hydroxyl groups (—OH) are attached to the surface of the hollow particles 11 made of silica shell, and in FIG. 4, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, by reacting TEIS2 as a surface modifier for 1 hour at a critical temperature (234.9 ° C.) and a critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent, The surface of the hollow particle 11 in which all three of the ethoxy groups of TEIS2 are made of silica shells, freely entering between the hollow particles 11 made of silica shells in which n-hexane is in a supercritical state and agglomerated as secondary particles. Then, it is condensed with the hydroxyl group and bonded to the surface of the hollow particle 11 made of silica shell.

  Thus, the surface of the hollow particles 11 made of silica is covered with TEIS2 as shown in FIG. 4 by the reaction of the innumerable hydroxyl groups on the surface of the hollow particles 11 made of silica with the TEIS2. Surface modified particles 12 according to the second exemplary embodiment are formed. As a result, the hollow particles 11 made of silica shells that have been aggregated as secondary particles are dispersed to form primary particles, which are not easily aggregated and easily dispersed, but the isocyanate groups react with the active groups of the organic resin. By making a strong bond with the organic resin, the surface-modified particles 12 can be more easily uniformly dispersed in the organic resin.

  A specific example of application of the surface modified particles 12 will be further described with reference to FIG. As shown in FIG. 4, the surface modified particles 12 according to the second embodiment having an isocyanate group are reacted with a block polyisocyanate 13 at a temperature (curing temperature) at which the block (BL) is removed in a xylene solvent.

  As a result, the block (BL) of the block-type polyisocyanate 13 is removed, the isocyanate group reacts with the isocyanate group of the surface-modified particle 12, and the hollow particles 11 made of silica shells having urethane bonds and the polyisocyanate 14 The bonded body 6 is formed, and the coated hollow silica particles 15 in which the surface modified particles 12 are uniformly and firmly coated with the polyisocyanate 14 are formed.

FIG. 5 shows the IR (infrared spectral absorption) spectrum of the surface modified particles 12 according to the second embodiment in comparison with the unmodified particles (hollow particles made of silica shells) 11 and the coated hollow silica particles 15. Is. As shown in FIG. 5, the unmodified particles 11 show absorption due to Si—OH bonds due to innumerable hydroxyl groups on the silica surface, whereas the surface modified particles 12 no longer absorb due to Si—OH bonds. Thus, the absorption due to the —CH ₂ — bond and the isocyanate group (—N═C═O) present in TEIS ₂ is very prominent.

  Furthermore, in the coated hollow silica particles 15, the isocyanate groups of the surface modified particles 12 and the block type polyisocyanate 13 are bonded to each other, so that the peak height of absorption due to the isocyanate groups (-N = C = O) is slightly lowered. Further, the absorption of —OH group, —NH— group, and C═O group derived from carbamic acid caused by the reaction of an isocyanate group with water is increased.

  In this way, in the surface modified particles 12 according to the second embodiment, in the supercritical state of n-hexane, TEIS2 is reacted with innumerable hydroxyl groups on the surface of the hollow particles 11 made of silica shells. The surface of the hollow particle 11 made of the shell is covered with TEIS2. As a result, the hollow particles 11 made of silica shells that have been aggregated as secondary particles are dispersed to form primary particles, which are difficult to aggregate and are easily dispersed.

  Furthermore, the block of the block type polyisocyanate 13 is released by reacting the surface modified particles 12 according to the second embodiment with the block type polyisocyanate 13 at a temperature at which the block is released (curing temperature) in a xylene solvent. The isocyanate group and the isocyanate group of the surface modified particles 12 react to form a conjugate 6 of the hollow particles 11 made of silica shells having urethane bonds and the polyisocyanate 14, and the surface modified particles 12 are polyisocyanate 14. Coated hollow silica particles 15 that are uniformly and firmly coated are formed.

Embodiment 3
Next, the surface modification particles and the surface modification method of fine inorganic particles according to the third embodiment of the present invention will be described with reference to FIG. FIG. 6 is a schematic diagram illustrating a surface modification particle manufacturing process and a fine inorganic particle surface modification method according to a third embodiment of the present invention.

  As shown in FIG. 6, in the surface modified particles 18 according to the third embodiment, the colloidal silica 1 having an average particle diameter of 40 nm is used as the fine inorganic particles as in the first embodiment. As an amino compound, 3-aminopropyltriethoxysilane (hereinafter also referred to as “TEAS”) 17 is used. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 6, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, by reacting TEAS17 as a surface modifier for 1 hour at the critical temperature (234.9 ° C.) and critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent, n-hexane enters a supercritical state and freely enters between colloidal silica 1 aggregated as secondary particles, and all three ethoxy groups of TEAS 17 undergo a condensation reaction with the hydroxyl groups on the surface of colloidal silica 1, thereby colloidal. Bonds to the surface of silica 1.

  As described above, the surface of the colloidal silica 1 is covered with the TEAS 17 as shown in FIG. 6 due to the reaction of the innumerable hydroxyl groups on the surface of the colloidal silica 1 with the TEAS 17. The modified particles 18 are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse, but the amino group reacts with the active group of the organic resin and is strongly bonded to the organic resin. By forming a simple bond, the surface modified particles 18 that are more easily uniformly dispersed in the organic resin are obtained.

Embodiment 4
Next, the surface modification particle and the surface modification method of fine inorganic particles according to the fourth embodiment of the present invention will be described with reference to FIG. FIG. 7 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 4 of the present invention.

  As shown in FIG. 7, in the surface modified particles 23 according to the fourth embodiment, the colloidal silica 1 having an average particle diameter of 40 nm is used as the fine inorganic particles as in the first and third embodiments. Vinyl triethoxysilane 22 which is a vinyl compound is used as a modifier. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 7, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  In contrast, vinyltriethoxysilane 22 as a surface modifier was reacted for 1 hour at the critical temperature (234.9 ° C.) and critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent. As a result, n-hexane enters a supercritical state and freely enters between colloidal silica 1 aggregated as secondary particles, so that all three ethoxy groups of vinyltriethoxysilane 22 are on the surface of colloidal silica 1. It is condensed with the hydroxyl group of and bonded to the surface of the colloidal silica 1.

  In this way, by reacting innumerable hydroxyl groups on the surface of the colloidal silica 1 and the vinyltriethoxysilane 22, the surface of the colloidal silica 1 is covered with the vinyltriethoxysilane 22 as shown in FIG. Surface modified particles 23 according to the fourth embodiment are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse, but the vinyl group reacts with the active group of the organic resin and strongly binds to the organic resin. By forming a simple bond, the surface modified particles 23 that are more easily uniformly dispersed in the organic resin are obtained.

  Further, since the vinyl group is a UV functional group that reacts with ultraviolet rays (UV), by using the surface-modified particles 23 according to the fourth embodiment, various surface-modified particles 23 that are cured in response to ultraviolet rays can be used. It can be applied to applications.

Embodiment 5
Next, the surface modification particles and the surface modification method of fine inorganic particles according to the fifth embodiment of the present invention will be described with reference to FIG. FIG. 8 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 5 of the present invention.

  As shown in FIG. 8, in the surface modified particles 26 according to the fifth embodiment, colloidal silica 1 having an average particle diameter of 40 nm is used as the fine inorganic particles as in the first, third, and fourth embodiments. As a surface modifier, 3-glycidoxypropyltriethoxysilane 25, which is an epoxy compound, is used. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 8, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, 3-glycidoxypropyltriethoxysilane 25 as a surface modifier, n-hexane as a solvent in an autoclave, n-hexane critical temperature (234.9 ° C.), critical pressure (3.02 MPa) ) For 1 hour, n-hexane is in a supercritical state and freely enters the colloidal silica 1 aggregated as secondary particles, and the ethoxy group of 3-glycidoxypropyltriethoxysilane 25 All of these are condensed with hydroxyl groups on the surface of the colloidal silica 1 and bonded to the surface of the colloidal silica 1.

  In this way, the surface of colloidal silica 1 reacts with 3-glycidoxy as shown in FIG. 8 by the reaction of the innumerable hydroxyl groups on the surface of colloidal silica 1 and 3-glycidoxypropyltriethoxysilane 25. Covered with propyltriethoxysilane 25, surface modified particles 26 according to the fifth embodiment are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse. In addition, the epoxy group reacts with the active group of the organic resin and is strong with the organic resin. By forming a simple bond, the surface modified particles 26 that are more easily uniformly dispersed in the organic resin can be obtained.

Embodiment 6
Next, the surface modification particle and the surface modification method of fine inorganic particles according to the sixth embodiment of the present invention will be described with reference to FIG. FIG. 9 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 6 of the present invention.

  As shown in FIG. 9, in the surface modified particles 28 according to the sixth embodiment, hollow particles 11 made of silica shells having a particle diameter of about 50 nm to about 100 nm are used as fine inorganic particles as in the second embodiment. As the surface modifier, 3-glycidoxypropyltriethoxysilane 25, which is an epoxy compound, is used as in the fifth embodiment. Numerous hydroxyl groups (—OH) are attached to the surface of the hollow particles 11 made of silica shell, and FIG. 9 shows only three of the innumerable hydroxyl groups so that the reaction can be easily understood.

  On the other hand, 3-glycidoxypropyltriethoxysilane 25 as a surface modifier, n-hexane as a solvent in an autoclave, n-hexane critical temperature (234.9 ° C.), critical pressure (3.02 MPa) ) For 1 hour, n-hexane is in a supercritical state, and freely enters between the hollow particles 11 made of silica shells that are aggregated as secondary particles, to give 3-glycidoxypropyltriethoxysilane. All three of the 25 ethoxy groups undergo a condensation reaction with the hydroxyl groups on the surface of the hollow particles 11 made of silica shell, and bind to the surfaces of the hollow particles 11 made of silica shell.

  In this way, by reacting innumerable hydroxyl groups on the surface of the hollow particles 11 made of silica shells and 3-glycidoxypropyltriethoxysilane 25, as shown in FIG. 9, the hollow particles 11 made of silica shells. The surface is covered with 3-glycidoxypropyltriethoxysilane 25 to form surface modified particles 28 according to the sixth embodiment. As a result, the hollow particles 11 made of silica shells that have been aggregated as secondary particles are dispersed into primary particles, which are not easily aggregated and easily dispersed, but the epoxy groups react with the active groups of the organic resin. By making a strong bond with the organic resin, the surface modified particles 28 that are more easily uniformly dispersed in the organic resin are obtained.

Embodiment 7
Next, the surface modification particle and the surface modification method of fine inorganic particles according to the seventh embodiment of the present invention will be described with reference to FIG. FIG. 10 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 7 of the present invention.

  As shown in FIG. 10, in the surface modified particles 31 according to the seventh embodiment, colloidal silica 1 having an average particle diameter of 40 nm is used as the fine inorganic particles as in the first, third, fourth, and fifth embodiments. In addition, 3-methacryloxypropyltriethoxysilane 30 which is a methacryloxy-based compound is used as a surface modifier. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 10, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  In contrast, 3-methacryloxypropyltriethoxysilane 30 as a surface modifier, n-hexane as a solvent in an autoclave, n-hexane critical temperature (234.9 ° C.), critical pressure (3.02 MPa) In the reaction, the n-hexane is brought into a supercritical state and freely enters between the colloidal silica 1 aggregated as secondary particles, and 3 of the ethoxy group of 3-methacryloxypropyltriethoxysilane 30 is obtained. All of them are condensed with hydroxyl groups on the surface of the colloidal silica 1 and bonded to the surface of the colloidal silica 1.

  In this way, the reaction of the innumerable hydroxyl groups on the surface of colloidal silica 1 and 3-methacryloxypropyltriethoxysilane 30 causes the surface of colloidal silica 1 to become 3-methacryloxypropyltrimethyl, as shown in FIG. Covered with ethoxysilane 30, surface modified particles 31 according to the seventh embodiment are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse. In addition, the methacryloxy group reacts with the active group of the organic resin and is strongly bonded to the organic resin. By forming a simple bond, the surface modified particles 31 that are more easily dispersed uniformly in the organic resin are obtained.

Embodiment 8
Next, the surface modification particle and the surface modification method of fine inorganic particles according to the eighth embodiment of the present invention will be described with reference to FIG. FIG. 11 is a schematic diagram illustrating a surface-modified particle manufacturing process and a fine inorganic particle surface modification method according to Embodiment 8 of the present invention.

  As shown in FIG. 11, in the surface modified particles 33 according to the eighth embodiment, colloidal silica 1 having an average particle diameter of 40 nm is used as fine inorganic particles as in the first, third, fourth, fifth, and seventh embodiments. As a surface modifier, butyltriethoxysilane 32, which is a compound having an alkyl group, is used. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 11, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  In contrast, butyltriethoxysilane 32 as a surface modifier was reacted for 1 hour at the critical temperature (234.9 ° C.) and critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent. As a result, n-hexane enters a supercritical state and freely enters between colloidal silica 1 aggregated as secondary particles, so that all three ethoxy groups of butyltriethoxysilane 32 are on the surface of colloidal silica 1. It is condensed with the hydroxyl group of and bonded to the surface of the colloidal silica 1.

  In this way, by reacting innumerable hydroxyl groups on the surface of the colloidal silica 1 and the butyltriethoxysilane 32, the surface of the colloidal silica 1 is covered with the butyltriethoxysilane 32 as shown in FIG. Surface modified particles 33 according to the eighth embodiment are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse. In addition, the butyl group that is an alkyl group has good compatibility with the organic resin. By uniformly dispersing in the resin, the surface modified particles 33 that are more easily uniformly dispersed in the organic resin are obtained.

Embodiment 9
Next, the surface modification particle and the surface modification method of fine inorganic particles according to the ninth embodiment of the present invention will be described with reference to FIG. FIG. 12 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 9 of the present invention.

  As shown in FIG. 12, in the surface modified particles 35 according to the ninth embodiment, colloidal particles having an average particle diameter of 40 nm are used as fine inorganic particles as in the first, third, fourth, fifth, seventh, and eighth embodiments. Silica 1 is used, and 3-acrylic acid propyltriethoxysilane 34, which is an acrylic compound, is used as a surface modifier. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 12, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, 3-acrylic acid propyltriethoxysilane 34 as a surface modifier, n-hexane as a solvent, n-hexane critical temperature (234.9 ° C.), critical pressure (3.02 MPa) In the reaction, the n-hexane is brought into a supercritical state and freely enters the colloidal silica 1 agglomerated as secondary particles, so that 3 of the ethoxy group of 3-propyl propyltriethoxysilane 34 is obtained. All of them are condensed with hydroxyl groups on the surface of the colloidal silica 1 and bonded to the surface of the colloidal silica 1.

  In this way, the reaction of the innumerable hydroxyl groups on the surface of the colloidal silica 1 and the 3-propyl propyltriethoxysilane 34 causes the surface of the colloidal silica 1 to become 3-propyl acrylate triacrylate as shown in FIG. Covered with ethoxysilane 34, surface modified particles 35 according to the ninth embodiment are formed. As a result, colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse. In addition, an acrylic acid group that is an organic acid reacts with an active group of an organic resin. By forming a strong bond with the organic resin, the surface modified particles 35 that are more easily uniformly dispersed in the organic resin are obtained.

Embodiment 10
Next, the surface modification particles and the surface modification method of fine inorganic particles according to the tenth embodiment of the present invention will be described with reference to FIG. FIG. 13 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 10 of the present invention.

  As shown in FIG. 13, in the surface modified particles 37 according to the tenth embodiment, the average particle size is 40 nm as fine inorganic particles, as in the first, third, fourth, fifth, seventh, eighth, and ninth embodiments. Colloidal silica 1 is used, and 3-imidopropyltriethoxysilane 36, which is an imide compound, is used as a surface modifier. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 13, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  In contrast, 3-imidopropyltriethoxysilane 36 as a surface modifier was used in an autoclave at n-hexane as a solvent at a critical temperature (234.9 ° C.) / Critical pressure (3.02 MPa) of n-hexane. By reacting for 1 hour, n-hexane enters a supercritical state and freely enters between colloidal silica 1 aggregated as secondary particles, and all three ethoxy groups of 3-imidopropyltriethoxysilane 36 are obtained. Reacts with a hydroxyl group on the surface of the colloidal silica 1 to bond to the surface of the colloidal silica 1.

  In this way, the surface of colloidal silica 1 reacts with 3-imidopropyltriethoxysilane as shown in FIG. 13 by the reaction of innumerable hydroxyl groups on the surface of colloidal silica 1 and 3-imidopropyltriethoxysilane 36. 36, the surface modified particles 37 according to the tenth embodiment are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse. In addition, the imide group reacts with the active group of the organic resin and is strongly bonded to the organic resin. By forming a simple bond, the surface modified particles 37 that are more easily uniformly dispersed in the organic resin are obtained.

Embodiment 11
Next, the surface modification particles and the surface modification method of fine inorganic particles according to the eleventh embodiment of the present invention will be described with reference to FIG. FIG. 14 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 11 of the present invention.

  As shown in FIG. 14, in the surface modified particles 39 according to the eleventh embodiment, average fine particles are formed as fine inorganic particles in the same manner as in the first, third, fourth, fifth, seventh, eighth, ninth, and tenth embodiments. Colloidal silica 1 having a diameter of 40 nm is used, and 3-phenylpropyltriethoxysilane 38, which is a compound having a phenyl group as an aryl group, is used as a surface modifier. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 14, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, 3-phenylpropyltriethoxysilane 38 as a surface modifier is 1 at a critical temperature (234.9 ° C.) and a critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent. By reacting for a period of time, n-hexane enters a supercritical state and freely enters between colloidal silica 1 aggregated as secondary particles, and all three ethoxy groups of 3-phenylpropyltriethoxysilane 38 are colloidal. A condensation reaction occurs with the hydroxyl group on the surface of the silica 1 to bond to the surface of the colloidal silica 1.

  In this way, the innumerable hydroxyl groups on the surface of the colloidal silica 1 react with the 3-phenylpropyltriethoxysilane 38, so that the surface of the colloidal silica 1 becomes 3-phenylpropyltriethoxysilane 38 as shown in FIG. Covered, surface modified particles 39 according to the eleventh embodiment are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse, but the phenyl group reacts with the active group of the organic resin and is strongly bonded to the organic resin. By forming a simple bond, the surface modified particles 39 that are more easily dispersed uniformly in the organic resin are obtained.

  In particular, when mixing in an aromatic organic resin, the aromatic organic resin and the phenyl group have good compatibility, and thus the surface-modified particles 39 are uniformly dispersed in the aromatic organic resin. In addition, since the phenyl group is extremely compatible with aromatic hydrocarbon solvents such as toluene and xylene, the surface modified particles 39 are easily dispersed uniformly in an organic solvent such as toluene and xylene.

Embodiment 12
Next, the surface modification particles and the surface modification method of fine inorganic particles according to the twelfth embodiment of the present invention will be described with reference to FIG. FIG. 15 is a schematic view showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 12 of the present invention.
As shown in FIG. 15, in the surface-modified particles 41 according to the twelfth embodiment, hollow particles 11 made of silica shells having a particle diameter of about 50 nm to about 100 nm are formed as fine inorganic particles in the same manner as in the second and sixth embodiments. As a surface modifier, methyltriethoxysilane 40 is used. Numerous hydroxyl groups (—OH) are attached to the surface of the hollow particles 11 made of silica shell, and in FIG. 15, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  In contrast, methyltriethoxysilane 40 as a surface modifier is reacted for 1 hour at the critical temperature (234.9 ° C.) and critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent. As a result, n-hexane enters a supercritical state and freely enters between hollow particles 11 made of silica shells that are aggregated as secondary particles, so that all three ethoxy groups of methyltriethoxysilane 40 are silica. It condenses with a hydroxyl group on the surface of the hollow particle 11 made of a shell and binds to the surface of the hollow particle 11 made of a silica shell.

  In this way, by reacting innumerable hydroxyl groups on the surface of the hollow particles 11 made of silica shells and methyltriethoxysilane 40, the surface of the hollow particles 11 made of silica shells is converted to methyltriethoxy as shown in FIG. Covered with ethoxysilane 40, surface modified particles 41 according to the twelfth embodiment are formed. As a result, the hollow particles 11 made of silica shells that have been aggregated as secondary particles are dispersed to form primary particles, which are not easily aggregated and easily dispersed, but the methyl groups react with the active groups of the organic resin. By making a strong bond with the organic resin, the surface modified particles 41 that are more easily uniformly dispersed in the organic resin are obtained.

Embodiment 13
Next, the surface modification particle and the surface modification method of fine inorganic particles according to the thirteenth embodiment of the present invention will be described with reference to FIG. FIG. 16 is a schematic diagram showing the surface-modified particle manufacturing process and the fine inorganic particle surface-modifying method according to Embodiment 13 of the present invention.

  As shown in FIG. 16, in the surface modified particles 45 according to the thirteenth embodiment, the fine inorganic particles are the same as in the first, third, fourth, fifth, seventh, eighth, ninth, tenth, and eleventh embodiments. Colloidal silica 1 having an average particle diameter of 40 nm is used, and 3-para-styrylpropyltrimethoxysilane 44 is used as a surface modifier. The surface of the colloidal silica 1 has innumerable hydroxyl groups (—OH), and in FIG. 16, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, 3-para-styrylpropyltrimethoxysilane 44 as a surface modifier was used in an autoclave using n-hexane as a solvent, and the critical temperature (234.9 ° C.) and critical pressure (3.02 MPa) of n-hexane. ) For 1 hour, n-hexane is in a supercritical state and freely enters the colloidal silica 1 aggregated as secondary particles, and the methoxy group of 3-para-styrylpropyltrimethoxysilane 44 All of these are condensed with hydroxyl groups on the surface of the colloidal silica 1 and bonded to the surface of the colloidal silica 1.

  In this way, the reaction of innumerable hydroxyl groups on the surface of the colloidal silica 1 and 3-para-styrylpropyltrimethoxysilane 44 causes the surface of the colloidal silica 1 to become 3-para-styryl as shown in FIG. Covered with propyltrimethoxysilane 44, surface modified particles 45 according to the thirteenth embodiment are formed. As a result, the colloidal silica 1 aggregated as secondary particles is dispersed to form primary particles, which are not easily aggregated and easy to disperse. In addition, the styryl group reacts with the active group of the organic resin and is strongly bonded to the organic resin. By forming a simple bond, the surface modified particles 45 that are more easily uniformly dispersed in the organic resin are obtained.

  In particular, when mixed in an aromatic organic resin, the aromatic organic resin and the styryl group have good compatibility, and thus the surface modified particles 45 are uniformly dispersed in the aromatic organic resin. Further, since the styryl group is extremely compatible with aromatic hydrocarbon solvents such as toluene and xylene, the surface-modified particles 45 are easily dispersed uniformly in an organic solvent such as toluene and xylene. Further, since the styryl group is a UV functional group that reacts with ultraviolet rays (UV), by using the surface modified particles 45 according to the thirteenth embodiment, various surface modified particles 45 that are cured in response to ultraviolet rays can be used. It can be applied to applications.

Embodiment 14
Next, the surface modification method of the surface modification particle | grains and fine inorganic particle concerning Embodiment 14 of this invention are demonstrated with reference to FIG. FIG. 17 (a) is a schematic diagram showing the surface-modified particle manufacturing process and fine inorganic particle surface modification method according to Embodiment 14 of the present invention, and (b) is the surface-modified particle according to Embodiment 14 of the present invention. It is a schematic diagram which shows the application by ultraviolet irradiation reaction.

  As shown in FIG. 17A, in the surface-modified particles 48 according to the fourteenth embodiment, silica shells having a particle diameter of about 50 nm to about 100 nm are formed as fine inorganic particles in the same manner as in the second, sixth, and twelfth embodiments. The hollow particles 11 are used, and acryloxypropyltrimethoxysilane 47 is used as the surface modifier. Numerous hydroxyl groups (—OH) are attached to the surface of the hollow particles 11 made of silica shell, and in FIG. 17, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, acryloxypropyltrimethoxysilane 47 as a surface modifier is 1 at the critical temperature (234.9 ° C.) and critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent. By reacting for a period of time, n-hexane enters a supercritical state, and freely enters between hollow particles 11 made of silica shells that are aggregated as secondary particles, so that 3 of the methoxy group of acryloxypropyltrimethoxysilane 47 All of them are subjected to a condensation reaction with the hydroxyl groups on the surface of the hollow particles 11 made of silica shell, and bonded to the surfaces of the hollow particles 11 made of silica shell.

  In this way, by reacting the innumerable hydroxyl groups on the surface of the hollow particles 11 made of silica shells and acryloxypropyltrimethoxysilane 47, as shown in FIG. 17A, the hollow particles 11 made of silica shells 11 are reacted. Are covered with acryloxypropyltrimethoxysilane 47 to form surface modified particles 48 according to the fourteenth embodiment.

 As a result, the hollow particles 11 made of silica shells that have been aggregated as secondary particles are dispersed to form primary particles, which are not easily aggregated and easily dispersed, but the acryloxy group reacts with the active group of the organic resin. By making a strong bond with the organic resin, the surface modified particles 48 that are more easily uniformly dispersed in the organic resin are obtained. In addition, since the acryloxy group is a UV functional group that reacts with ultraviolet rays (UV), by using the surface modified particles 48 according to the fourteenth embodiment, various surface modified particles 48 that are cured in response to ultraviolet rays can be used. It can be applied to applications.

  As shown in FIG. 17B, the surface-modified particles 48 thus manufactured are irradiated with ultraviolet rays (UV) by adding a polyfunctional acrylate compound 49 and an acetophenone-based photoradical polymerization initiator. As a result, the double bond between the acryloxy group and the polyfunctional acrylate compound 49 is radicalized, and a three-dimensional cross-linking reaction occurs by a radical chain reaction to form a three-dimensional cross-linked body 50. In this way, by using the surface modified particles 48 having an acryloxy group that is a UV functional group, the three-dimensional crosslinked body 50 can be formed by ultraviolet (UV) irradiation.

Embodiment 15
Next, the surface modification particles and the surface modification method of fine inorganic particles according to the fifteenth embodiment of the present invention will be described with reference to FIG. FIG. 18 (a) is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface modification method according to Embodiment 15 of the present invention, and (b) is a surface modified particle according to Embodiment 15 of the present invention. It is a schematic diagram which shows the application by ultraviolet irradiation reaction.

  As shown in FIG. 18 (a), in the surface-modified particles 52 according to the fifteenth embodiment, the fine inorganic particles have a particle size of about 50 nm to about 100 nm as in the second, sixth, twelfth, and fourteenth embodiments. Hollow particles 11 made of silica shell are used, and methyltrimethoxysilane 51 is used as a surface modifier. Numerous hydroxyl groups (—OH) are attached to the surface of the hollow particles 11 made of silica shell, and in FIG. 18A, only one of the numerous hydroxyl groups is shown for easy understanding of the reaction. Yes.

  In contrast, methyltrimethoxysilane 51 as a surface modifier was reacted for 1 hour at the critical temperature (234.9 ° C.) and critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent. As a result, n-hexane enters a supercritical state and freely enters between hollow particles 11 made of silica shells that are aggregated as secondary particles, and one of the three methoxy groups of methyltrimethoxysilane 51 is It condenses with the hydroxyl groups on the surface of the hollow particles 11 made of silica shell, and binds to the surfaces of the hollow particles 11 made of silica shell. The other two methoxy groups react with each other with methyltrimethoxysilane 51 to form surface modified particles 52 as shown in FIG.

  In this way, by reacting the innumerable hydroxyl groups on the surface of the hollow particles 11 made of silica shells with methyltrimethoxysilane 51, the surface of the hollow particles 11 made of silica shells as shown in FIG. 18 (a). Are covered with methyltrimethoxysilane 51 to form surface-modified particles 52 according to the fifteenth embodiment. As a result, the hollow particles 11 made of silica shells that have been aggregated as secondary particles are dispersed to form primary particles, which are not easily aggregated and easily dispersed, but also methyl groups and methoxy groups are bonded to the active groups of the organic resin. By reacting and forming a strong bond with the organic resin, the surface modified particles 52 that are more easily uniformly dispersed in the organic resin are obtained.

  As shown in FIG. 18B, the surface-modified particles 52 thus manufactured are irradiated with ultraviolet rays (UV) by adding a polyfunctional alkoxysilane compound 53 and a sulfonium salt-based photocationic polymerization initiator. As a result, a protonic acid is generated from the photocationic polymerization initiator, and the alkoxysilyl group of the polyfunctional alkoxysilane compound 53 is hydrolyzed to generate a silanol group. As a result, a three-dimensional crosslinking reaction occurs, and a three-dimensional crosslinked body 54 is formed. In this way, by using the surface modified particles 52 having a methoxy group that is a UV functional group, the three-dimensional crosslinked body 54 can be formed by ultraviolet (UV) irradiation.

  In each of the above embodiments, only the case where the surface of the hollow particles 11 made of the colloidal silica 1 and the silica shell has been described as the fine inorganic particles, but the present invention is not limited thereto, and the range is from about 10 nm to about 300 nm. If it is the fine inorganic particle which has an inside particle diameter, it can surface-modify various fine inorganic particles to make a surface modified particle.

  In each of the above embodiments, only the case where n-hexane is used as the organic solvent has been described. However, the present invention is not limited to this, and other organic solvents such as aliphatic alcohols such as methanol, ethanol, and propanol are used. Aromatic hydrocarbons such as xylene can be used.

  In practicing the present invention, the composition, components, shape, quantity, material, size, manufacturing method, etc. of other parts of the surface-modified particles, and other steps of the surface modification method of fine inorganic particles, The present invention is not limited to the above embodiments.

FIG. 1 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 1 of the present invention. FIG. 2 is a schematic diagram showing Example 1 of the application method of the surface-modified particles according to the first embodiment of the present invention. FIG. 3 is a schematic diagram showing Example 2 of the application method of the surface-modified particles according to the first embodiment of the present invention. FIG. 4 is a schematic diagram showing a surface-modified particle manufacturing process, a fine inorganic particle surface-modifying method, and an application example of the surface-modified particle according to the second embodiment of the present invention. FIG. 5 is a diagram showing the IR (infrared spectral absorption) spectrum of the surface-modified particles according to the second embodiment of the present invention compared with unmodified particles and coated particles. FIG. 6 is a schematic diagram illustrating a surface modification particle manufacturing process and a fine inorganic particle surface modification method according to a third embodiment of the present invention. FIG. 7 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 4 of the present invention. FIG. 8 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 5 of the present invention. FIG. 9 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 6 of the present invention. FIG. 10 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 7 of the present invention. FIG. 11 is a schematic diagram illustrating a surface-modified particle manufacturing process and a fine inorganic particle surface modification method according to Embodiment 8 of the present invention. FIG. 12 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 9 of the present invention. FIG. 13 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 10 of the present invention. FIG. 14 is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 11 of the present invention. FIG. 15 is a schematic view showing a surface-modified particle manufacturing process and a fine inorganic particle surface-modifying method according to Embodiment 12 of the present invention. FIG. 16 is a schematic diagram showing the surface-modified particle manufacturing process and the fine inorganic particle surface-modifying method according to Embodiment 13 of the present invention. FIG. 17 (a) is a schematic diagram showing the surface-modified particle manufacturing process and fine inorganic particle surface modification method according to Embodiment 14 of the present invention, and (b) is the surface-modified particle according to Embodiment 14 of the present invention. It is a schematic diagram which shows the application by ultraviolet irradiation reaction. FIG. 18 (a) is a schematic diagram showing a surface-modified particle manufacturing process and a fine inorganic particle surface modification method according to Embodiment 15 of the present invention, and (b) is a surface modified particle according to Embodiment 15 of the present invention. It is a schematic diagram which shows the application by ultraviolet irradiation reaction.

1 Fine inorganic particles 2, 17, 22, 25, 30, 32, 34, 36, 38, 40, 44, 47, 51 Surface modifiers 3, 12, 18, 23, 26, 28, 31, 33, 35, 37, 39, 41, 45, 48, 52 Surface-modified particles 11 Nano hollow particles made of silica shell 15 Coated hollow silica particles

Claims (6)

Surface-modified particles obtained by surface-modifying fine inorganic particles of hollow particles made of silica shells having an outer diameter in the range of 20 nm to 130 nm ,
A mixture is prepared by adding an organic solvent and a surface modifier to the fine inorganic particles, and a high-temperature and high-pressure state is applied to the mixture as a supercritical state of the organic solvent to add the surface modifier to the surface of the fine inorganic particles. Let me
The surface-modified particle, wherein the surface modifier is any one of an isocyanate compound, a compound having an alkyl group, a compound having an aryl group, and a compound having a UV functional group . The surface-modified particles according to claim 1, wherein the supercritical state of the organic solvent that applies high temperature and pressure to the mixture is performed using an autoclave .   The surface modified particles according to claim 1, wherein the organic solvent is n-hexane. A surface modification method for fine inorganic particles of hollow particles comprising a silica shell having an outer diameter in the range of 20 nm to 130 nm ,
Adding an organic solvent and a surface modifier to the fine inorganic particles to produce a mixture;
Reacting and adding the surface modifier to the surface of the fine inorganic particles as a supercritical state of the organic solvent by applying high temperature and pressure to the mixture ,
The method for modifying the surface of fine inorganic particles , wherein the surface modifier in the step is any one of an isocyanate compound, a compound having an alkyl group, a compound having an aryl group, and a compound having a UV functional group . The method for modifying the surface of fine inorganic particles according to claim 4, wherein the step of applying high temperature and pressure to the mixture is performed using an autoclave. The organic solvent, the surface modification method of the fine inorganic particles according to claim 4 or claim 5 characterized in that it is a n- hexane.

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