JP2010084070A - Hollow particle-containing master batch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To further extend the application field of silica nano hollow particles and make the use of them easier by preventing the cohesion of the silica nano hollow particles for dispersing them as micro-aggregated particles with an organic synthetic resin and enabling the mixing of them by a larger amount as a solid part in a hollow particle-containing master batch. <P>SOLUTION: The hollow particles are prepared by (S10) blending the silica nano hollow particles 1 with ethanol and a modified silicone oil as a surface-modifying agent, (S11) agitating and dispersing by using a high speed agitator, (S12) dispersing huge aggregated particles aggregated to approximately 5 μm particle diameter and then filtered by using a sieve, and then (S13) dispersing by using a wet type jet mill strongly to make the micro-aggregated particles having approximately ≤0.5 μm particle diameter. The hollow particle-containing master batch 10 is produced by (S17) heating and kneading the dispersive silica nano hollow particles 5 prepared by further passing through three processes with the organic synthetic resin 6, (S18) extrusion molding and (S19) pelletizing. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention increases the amount of nano hollow particles composed of silica shells having an outer diameter in the range of approximately 30 nm to approximately 300 nm (hereinafter also referred to as “silica nano hollow particles”) into the organic synthetic resin. The present invention relates to a hollow particle-containing master batch that is easier to use.

  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. As an example, there is an invention of highly dispersed silica nano hollow particles described in Patent Document 1 and a method for producing the same. This silica nano hollow particle is a nano hollow particle composed of a dense silica shell, in which pores of 2 nm to 20 nm are not detected in the pore distribution, and the first step of adjusting calcium carbonate is coated with silica. It is produced by the second step, a third step in which calcium carbonate is dissolved to form silica nano hollow particles.

The highly dispersed silica nano hollow particles according to Patent Document 1 are hollow and have a thin silica shell, so that they have excellent heat insulating properties and transparency. As shown in Patent Document 2, they are uniform in paints, films, and synthetic fibers. By disperse in the composition, it is possible to obtain a heat insulating paint, heat insulating film, and heat insulating fiber, which can be applied to a wide range of technical fields. In addition, various applications are expected. In order to further expand this application field and facilitate the use of silica nano hollow particles, it is desired to be supplied as a masterbatch as shown in Patent Documents 3 and 4.
JP 2005-263550 A JP 2007-070458 A JP 2006-176750 A JP 2007-277433 A

  However, since the highly dispersed silica nano hollow particles described in Patent Document 1 are fine particles having an outer diameter of about 30 nm to about 300 nm, they are likely to agglomerate and melt even in a solvent such as water or an organic solvent. Even when mixed in organic synthetic resin, it immediately agglomerates into huge agglomerated particles with a size of several to several tens of μm, and fine agglomerates with a size of several hundred nm in paints, films, and synthetic fibers. Since it is practically difficult to uniformly disperse the particles, excellent properties such as heat insulation, transparency, and low dielectric constant of the silica nano hollow particles cannot be sufficiently exhibited.

In addition, nano hollow particles made of silica shell have a very large specific surface area of about 150 m ² / g, so that even if they are mixed in paints or molten organic synthetic resins, only a small percentage by weight can be mixed. could not. This large specific surface area value is presumed to be due to the presence of fine irregularities at the molecular level on the surface of the nano hollow particles made of silica shells. For this reason, there existed a problem that it was difficult to supply as a masterbatch as shown by the said patent document 3 and the patent document 4. FIG.

  Therefore, the present invention prevents silica nano hollow particles from agglomerating, disperses them as fine agglomerated particles in an organic synthetic resin, and allows a larger amount to be mixed as a solid content, thereby applying silica nano hollow particles. An object of the present invention is to provide a hollow particle-containing masterbatch capable of further expanding the field and facilitating use.

  The hollow particle-containing masterbatch according to the invention of claim 1 is formed into a pellet by substantially uniformly dispersing nano hollow particles composed of silica shells having an outer diameter in a range of approximately 30 nm to approximately 300 nm in an organic synthetic resin. 20 wt% to 40 wt% of dispersible silica nanohollow particles in the organic synthetic resin, wherein the surface is modified by reacting the nanohollow particles comprising silica shell with a surface modifier. It is made to contain in the range of.

 Here, 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., modified silicone oils such as monoamine modified silicone oil and polyether modified silicone oil can be used.

 In the present invention, those with “substantially” added to the numerical value do not appear as the critical value or the boundary value, but the numerical value is regarded as an approximate value.

  The hollow particle-containing masterbatch according to the invention of claim 2 is the structure of claim 1, wherein the dispersible silica nanohollow particle is obtained by adding an organic solvent and the surface modifier to the nanohollow particle comprising the silica shell. In addition to being strongly dispersed by a mill, the surface is modified by reacting and adding the surface modifier to the nano hollow particles made of the silica shell.

 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 “wet jet mill”, a nanomizer manufactured by SG Engineering Co., Ltd., an ultra-high pressure homogenizer LAB2000 manufactured by SMT Co., Ltd., an optimizer manufactured by Sugino Machine Co., Ltd., or the like can be used. .

  The hollow particle-containing masterbatch according to the invention of claim 3 is the structure of claim 2, wherein the surface modification is performed by adding the organic solvent and the surface modifier to the nanohollow particles comprising the silica shell. The surface modifier is reacted and added to the surface of the hollow nanoparticle composed of the silica shell by applying high temperature and high pressure to the mixture to form a supercritical state of the organic solvent.

  The hollow particle-containing masterbatch according to a fourth aspect of the present invention is the master batch according to any one of the first to third aspects, wherein the organic synthetic resin is polyethylene or polypropylene.

  The hollow particle-containing masterbatch according to the invention of claim 1 is formed into a pellet by substantially uniformly dispersing nano hollow particles composed of silica shells having an outer diameter in a range of approximately 30 nm to approximately 300 nm in an organic synthetic resin. A dispersible silica nanohollow particle in a range of 20% by weight to 40% by weight in an organic synthetic resin, which is a masterbatch obtained by surface-modifying a nanohollow particle composed of silica shell by reaction addition of a surface modifier. And more preferably in the range of 30% to 40% by weight.

 Here, 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., modified silicone oils such as monoamine modified silicone oil and polyether modified silicone oil can be used.

Even if it is going to mix the nano hollow particle which consists of a silica shell which has the outside diameter in the range of about 30 nm-about 300 nm in the melted organic synthetic resin, in usual kneading machines, such as a lab plast mill and a kneader, It is difficult to disperse nano hollow particles composed of silica shells aggregated into giant aggregated particles of the order of several tens of μm into fine aggregated particles of the order of several hundred nm. Moreover, since the nano hollow particle which consists of a silica shell has a very large specific surface area of about 150 m < ² > / g, even if it tried to mix in the molten organic synthetic resin, only a small weight% could be mixed. . This large specific surface area value is presumed to be due to the presence of fine irregularities at the molecular level on the surface of the nano hollow particles made of silica shells.

  Therefore, it is assumed that the surface modification agent is added to the hollow nanoparticle composed of silica shell to modify the surface, and it is assumed that the surface modification agent fills the fine irregularities at the molecular level, and the specific surface area decreases. ing. By surface modification in this manner, the dispersibility of nano hollow particles made of silica shells is improved, and nano hollow particles made of finely dispersed silica shells do not easily reaggregate, and almost all The nano hollow particles made of silica shell are finely dispersed to obtain dispersible silica nano hollow particles which are fine agglomerated particles having an outer diameter of several hundred nm.

  The dispersible silica nano hollow particles obtained in this way are finely agglomerated without agglomerating into giant agglomerated particles even when mixed into molten organic synthetic resin because the periphery of the finely agglomerated particles is surface-modified with a surface modifier. It can mix in the state disperse | distributed to particle | grains. In addition, as described above, as a result of the reduction of the specific surface area, huge agglomerated particles on the order of several μm to several tens of μm are mixed even though they are mixed in finely agglomerated particles having an outer diameter of several hundred nm. A larger amount of silica nano hollow particles can be mixed than in the case of doing so.

  In this way, the silica nano hollow particles can be prevented from agglomerating and dispersed in the organic synthetic resin as fine agglomerated particles, and a larger amount can be mixed as a solid content, thereby enabling application fields of silica nano hollow particles. It becomes a hollow particle-containing masterbatch that can be further expanded and used easily.

  In the hollow particle-containing masterbatch according to the invention of claim 2, the dispersible silica nanohollow particles are strongly dispersed in a wet jet mill by adding an organic solvent and a surface modifier to the nanohollow particles composed of silica shells. Surface modification is performed by reacting and adding a surface modifying agent to nano hollow particles made of shells.

 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 “wet jet mill”, a nanomizer manufactured by SG Engineering Co., Ltd., an ultra-high pressure homogenizer LAB2000 manufactured by SMT Co., Ltd., an optimizer manufactured by Sugino Machine Co., Ltd., or the like can be used. .

 As described above, nano hollow particles made of silica shells having an outer diameter in the range of about 30 nm to about 300 nm are aggregated into giant aggregated particles of the order of several μm to several tens of μm. It is difficult to disperse the fine aggregated particles. Therefore, first, an organic solvent and a surface modifier are added, and strong stirring and dispersion are performed with a wet jet mill to finely disperse most of the nano hollow particles made of silica shells.

  Then, the surface is modified by reacting and adding a surface modifier to the nano hollow particles made of silica shell. By surface modification in this manner, the dispersibility of nano hollow particles made of silica shells is improved, and nano hollow particles made of finely dispersed silica shells do not easily reaggregate, and almost all Nano hollow particles made of silica shells are finely dispersed to form fine agglomerated particles having an outer diameter of several hundred nm. Dispersible silica nano hollow particles obtained by removing the solvent by drying or the like in this state are mixed with molten organic synthetic resin because the periphery of the fine aggregated particles is surface-modified with a surface modifier. Moreover, it can mix in the state disperse | distributed to the fine aggregated particle, without aggregating to a giant aggregated particle.

  In this way, the silica nano hollow particles can be prevented from agglomerating and dispersed in the organic synthetic resin as fine agglomerated particles, and a larger amount can be mixed as a solid content, thereby enabling application fields of silica nano hollow particles. It becomes a hollow particle-containing masterbatch that can be further expanded and used easily.

  In the hollow particle-containing masterbatch according to the invention of claim 3, the surface modification is performed by adding an organic solvent and a surface modifier to the nano hollow particles made of silica shell, and then applying high temperature and high pressure to the mixture to form the organic solvent. As a supercritical state, a surface modifier is reacted and added to the surface of the hollow nanoparticle made of silica shell.

  By setting the supercritical state of the organic solvent, the organic solvent freely enters between the aggregated particles together with the surface modifier, and the surface modifier is reactively added to the entire surface of the fine aggregated particles. For this reason, even if it performs powerful stirring and dispersion | distribution with a wet jet mill, each surface of the silica nano hollow particle which does not disperse | distribute to a fine aggregation particle but remains as a huge aggregation particle | grain can be surface-modified. Therefore, the operating conditions of the wet jet mill can be relaxed, and almost all silica nano hollow particles can be finely dispersed.

  In this way, the silica nano hollow particles can be prevented from agglomerating and dispersed in the organic synthetic resin as fine agglomerated particles, and a larger amount can be mixed as a solid content, thereby enabling application fields of silica nano hollow particles. It becomes a hollow particle-containing masterbatch that can be further expanded and used easily.

  In the hollow particle-containing masterbatch according to the invention of claim 4, the organic synthetic resin is polyethylene or polypropylene.

  Polyethylene (PE) and polypropylene (PP) are typical thermoplastic resins and general-purpose organic synthetic resins applied to a wide range of fields. Therefore, by manufacturing a masterbatch in which silica nano hollow particles are dispersed in a large amount in polyethylene or polypropylene, it can be applied to a wide range of application fields by mixing polyethylene or polypropylene alone with the masterbatch and performing various moldings. can do.

  Also, since polyethylene and polypropylene are good dispersibility of dispersible silica nano hollow particles and are inexpensive organic synthetic resins, a master batch in which relatively expensive silica nano hollow particles are dispersed is manufactured at a lower cost. It also has the advantage of being able to.

  In this way, the silica nano hollow particles can be prevented from agglomerating and dispersed in the organic synthetic resin as fine agglomerated particles, and a larger amount can be mixed as a solid content, thereby enabling application fields of silica nano hollow particles. It becomes a hollow particle-containing masterbatch that can be further expanded and used easily.

  Embodiments of the present invention will be described below with reference to the drawings. In each embodiment, the same symbol and the same reference sign mean the same or corresponding functional part, and the same sign and the same reference sign in the embodiments are the functional parts common to those embodiments. Therefore, the detailed description which overlaps is abbreviate | omitted here.

Embodiment 1
First, the hollow particle containing masterbatch which concerns on Embodiment 1 of this invention is demonstrated with reference to FIG.1 and FIG.2. FIG. 1 is a schematic diagram showing a process for producing nano hollow particles made of silica shells used for producing a hollow particle-containing master batch according to Embodiment 1 of the present invention. FIG. 2 is a flowchart showing a method for manufacturing a hollow particle-containing masterbatch according to Embodiment 1 of the present invention.

 Initially, the outline of the manufacturing method of the nano hollow particle which consists of a silica shell based on this invention is demonstrated with reference to FIG. As shown in FIG. 1, first, calcium carbonate fine particles 2 that become core particles are crystal-grown. The calcium carbonate crystal 2 produced here is calcite and is a hexagonal crystal system. However, by controlling the synthesis conditions, it is grown into a shape as if it is a cubic system, that is, a “cubic shape”. be able to. Here, the “cubic form” refers to a shape similar to a cube surrounded by a face, not limited to a cube. After crystal growth so that the outer diameter of the calcium carbonate 2 is 20 nm to 200 nm, the calcium carbonate fine particles 2 are coated with silica 3 using silicon alkoxide by a sol-gel method.

 Subsequently, this is dispersed in water, and an acid is added to dissolve and discharge the internal calcium carbonate 2, thereby forming nano hollow particles 4 composed of cubic shaped silica shells having outflow holes. Finally, nano hollow particles (silica nano hollow particles) 1 made of a dense silica shell are produced by closing the pores from which calcium carbonate 2 dissolved by baking at 800 ° C. flows out. The inner diameter of the hollow portion 1b of the silica nano hollow particle 1 is 20 nm to 200 nm of the outer diameter of the calcium carbonate fine particle 2 of the core particle, and the thickness of the dense silica shell 1a is 1 nm to 5 nm, even if it is thick, about 5 nm to 20 nm. Therefore, the outer diameter of the silica nano hollow particles 1 is approximately 30 nm to approximately 300 nm.

 Next, the manufacturing method of the hollow particle containing masterbatch which concerns on Embodiment 1 of this invention is demonstrated with reference to the flowchart of FIG. In the first embodiment, the silica nano-hollow particles are made of nano-sized silica shells having an average outer diameter of 70 nm and an outer diameter in a range of approximately 50 nm to 100 nm and a cubic shape of a silica shell having a porosity of approximately 70% to 80%. The hollow particles 1 are used.

 In the method for producing dispersible silica nano-hollow particles according to the first embodiment, as shown in FIG. 2, first, nano-hollow particles comprising a cubic-shaped silica shell produced by the production process described in FIG. 1 is blended with ethanol as an organic solvent and a modified silicone oil as a surface modifier in a predetermined blending amount (step S10), and stirred and dispersed with a high-speed stirrer (step S11).

 In the first embodiment, as a “high-speed stirrer”, T.M. K. A fill mix is used. Here, the aggregated giant aggregated particles are dispersed to a particle diameter of about 5 μm. Next, after this dispersion is filtered through a sieve (step S12), it is strongly dispersed by a wet jet mill to form fine agglomerated particles having a particle size of approximately 0.5 μm (500 nm) or less (step S13). . Here, as the “wet jet mill”, specifically, a nanomizer manufactured by SG Engineering Co., Ltd., an ultrahigh pressure homogenizer LAB2000 manufactured by SMT Co., Ltd., an optimizer manufactured by Sugino Machine Co., Ltd., Etc. can be used.

 Subsequently, the dispersion is applied to an evaporator to evaporate the solvent, and the concentration of the nano hollow particles 1 made of silica shells is concentrated from 2.5% by weight to 10% by weight (step S14). Thereafter, the moisture content is set to 3% or less with a vibration dryer (step S15), and further, the powder dryer is heated at 125 ° C. for 60 minutes to be dried (step S16). The dispersible silica nano hollow particles 5 according to the first embodiment are obtained through the above steps.

 Here, in the blending stage of step S10, hydrophilic silicone nano hollow particles having a hydrophilic dispersibility are obtained by using a modified silicone oil into which a hydrophilic organic group such as a polyether group, an ethoxy group or a carboxyl group is introduced as the modified silicone oil. 5 Therefore, when mixed and dispersed in an organic synthetic resin having a hydrophilic functional group, it can be easily dispersed as fine agglomerated particles without agglomeration simply by kneading with a normal heat kneader such as a kneader. In addition, a larger amount can be mixed, and the properties such as heat insulation and transparency of the silica nano hollow particles 1 can be sufficiently exhibited.

 On the other hand, by using a modified silicone oil into which a lipophilic organic group such as a monoamine group, an amino group, or an alkyl group is introduced as the modified silicone oil, the lipophilic dispersible silica nano hollow particles 5 are obtained. Therefore, when mixed and dispersed in an organic synthetic resin having a lipophilic functional group, it can be easily dispersed as fine agglomerated particles without agglomeration simply by kneading with a normal heat kneader such as a kneader. In addition, a larger amount can be mixed, and the properties such as heat insulation and transparency of the silica nano hollow particles 1 can be sufficiently exhibited.

 Such heat-kneading with the organic synthetic resin 6 is carried out in a kneader after thoroughly mixing the pellet-shaped organic synthetic resin 6 and the powdered dispersible silica nano hollow particles 5 in a dry state (step). S17). The molten organic synthetic resin 6 and the dispersible silica nano hollow particles 5 are kneaded so as to be sufficiently uniform by a kneader and then extruded by an extruder (step S18) and extruded from a die of the extruder. The obtained mixture is pelletized (step S19).

 Here, there are roughly two methods for pelletizing. One is a method called strand cutting, which is a method in which a mixture extruded into a thin rod shape from a die of an extruder is immediately cooled and solidified in water and cut into a cylindrical shape with a cutter. As a result, a large number of cylindrical pellets having an outer diameter of 1 mm to 3 mm and a length of 2 mm to 5 mm are manufactured. The other is a method called hot cut, in which a mixture extruded from a die of an extruder is immediately cut with a rotary blade and cooled and solidified in water. As a result, a large number of rice grain- or oval-shaped pellets having an outer diameter of about 1 mm to 2 mm and a length of about 1 mm to 2 mm are manufactured.

 Thus, the hollow particle-containing masterbatch 10 according to the first embodiment in which the dispersible silica nano hollow particles 5 are contained in the organic synthetic resin 6 in the range of 20 wt% to 40 wt% is manufactured. The

  In Example 1 of Embodiment 1, monoamine-modified silicone oil is used as the surface modifier, and low density polyethylene (LDPE) is used as the organic synthetic resin 6, according to the production process shown in FIG. A hollow particle-containing master batch 10 containing the dispersible silica nano hollow particles 5 at a high concentration of 35% by weight was produced. In the pelletization of step S19 in FIG. 2, low-density polyethylene tends to become a beautiful rod shape, and thus a cylindrical pellet having an outer diameter of about 1 mm and a length of about 2.5 mm was obtained by strand cutting.

  Since the hollow particle-containing masterbatch 10 contains the dispersible silica nano hollow particles 5 at a high concentration of 35% by weight, it is mixed with pellets of low density polyethylene alone 4 to 8 times by weight, and injection molding ( A surface layer of low-density polyethylene containing 4-8% by weight of dispersible silica nano hollow particles 5 is formed on the surface of a normal plastic molding by two-color molding or two-stage molding), or calendar molding Can form a low-density polyethylene film containing the dispersible silica nano hollow particles 8 at a ratio of 4 to 8% by weight.

  In such a product, since the dispersible silica nano hollow particles 5 are uniformly dispersed in the low density polyethylene, the characteristics of the silica nano hollow particles 1 such as heat insulation, transparency, and high dielectric constant are remarkably exhibited. It can be suitably used for applications requiring properties such as heat insulation, transparency, and high dielectric constant. And by supplying as the hollow particle containing masterbatch 10, content of the dispersible silica nano hollow particle 5 in a product can be set freely and correctly.

 Thus, in the hollow particle-containing masterbatch 10 according to the first embodiment, the silica nano hollow particles 1 are prevented from agglomerating and dispersed as fine agglomerated particles in the low density polyethylene 6 as the organic synthetic resin, and Further, by modifying the surface so that a larger amount can be mixed as a solid content, the application field of the silica nano hollow particles 1 can be further expanded and the use can be facilitated.

Embodiment 2
Next, the hollow particle-containing master batch according to the second embodiment will be described with reference to FIGS. FIG. 3 is a flowchart showing a method for manufacturing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention.

 FIG. 4 is a schematic diagram showing a specific example 1 of the surface modification method in the method for producing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention. FIG. 5 is a schematic diagram showing a specific example 2 of the surface modification method in the method for producing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention. FIG. 6 is a schematic diagram showing a specific example 3 of the surface modification method in the method for producing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention. FIG. 7 is a schematic diagram showing a specific example 4 of the surface modification method in the method for producing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention.

 As shown in FIG. 3, first, the nano hollow particles 1 made of the silica shell of the cubic shape manufactured by the manufacturing process described in FIG. 1 of the first embodiment are used as the organic solvent in a predetermined blending amount. It mix | blends with n-hexane and a surface modifier (step S20), and is stirred and disperse | distributed with a high-speed stirrer (step S21). Also in the second embodiment, the nano hollow particles 1 made of a silica shell having a cubic shape with an average outer diameter of 70 nm and an outer diameter in the range of about 50 nm to 100 nm and a porosity of about 70% to 80% are used. It was. Also in the second embodiment, as the “high-speed stirrer”, T.I. K. A fill mix is used.

  Here, the aggregated giant aggregated particles are dispersed to a particle diameter of about 5 μm. Next, after this dispersion is filtered through a sieve (step S22), it is strongly dispersed by a wet jet mill to form fine agglomerated particles having a particle size of about 0.5 μm or less (step S23). Here, as the “wet jet mill”, specifically, a nanomizer manufactured by SG Engineering Co., Ltd., an ultrahigh pressure homogenizer LAB2000 manufactured by SMT Co., Ltd., an optimizer manufactured by Sugino Machine Co., Ltd., Etc. can be used.

 Subsequently, the dispersion is applied to an evaporator to evaporate the solvent, and the concentration of the nano hollow particles 1 made of silica shell is concentrated from 2.5% by weight to 10% by weight (step S24). Then, by applying pressure and heating in an autoclave and reacting at a critical temperature (234.9 ° C.) / Critical pressure (3.02 MPa) of n-hexane for 1 hour, the surface modifier is converted into a supercritical state of n-hexane. The surface modification of the nano hollow particles 1 made of silica shell is performed (step S25).

 As a result, the nano hollow particles 1 made of silica shell are surface-modified with the surface modifier and pulverized to obtain the dispersible silica nano hollow particles 8 according to the second embodiment. Here, a specific example of the surface modification in step S25 of FIG. 3 will be described with reference to FIGS.

  In specific example 1 of the second embodiment shown in FIG. 4, triethoxypropyl isocyanate silane (TEIS) 12 which is an isocyanate compound is used as a surface modifier. In addition, the surface of the nano hollow particle 1 made of silica shell has an infinite number of hydroxyl groups (—OH), and in FIG. 4, only three of the innumerable hydroxyl groups are shown for easy understanding of the reaction. Yes.

  On the other hand, by reacting TEIS12 as a surface modifier for 1 hour at the critical temperature (234.9 ° C.) / Critical pressure (3.02 MPa) of n-hexane in an autoclave using n-hexane as a solvent, Nano hollow particles 1 in which all three ethoxy groups of TEIS 12 are composed of silica shells are freely inserted between nano hollow particles 1 composed of silica shells in which n-hexane is in a supercritical state and aggregated as giant agglomerated particles. Then, it condenses with the hydroxyl groups on the surface and binds to the surface of the nano hollow particles 1 made of silica shell.

  In this way, the surface of the nano hollow particle 1 made of silica shell is covered with TEIS 12 as shown in FIG. 4 by the reaction of innumerable hydroxyl groups on the surface of the nano hollow particle 1 made of silica shell with TEIS 12. Thus, the dispersible silica nano hollow particles 8 according to the first specific example of the second embodiment are formed. As a result, the nano hollow particles 1 composed of silica shells aggregated as giant aggregated particles on the order of several μm to several tens of μm are dispersed to form fine aggregated particles on the order of several hundreds of nm. In addition, when the isocyanate group reacts with the active group of the organic synthetic resin to form a strong bond with the organic synthetic resin, the dispersible silica nano hollow particles 8 that are more easily uniformly dispersed in the organic synthetic resin are obtained.

  Moreover, in the specific example 2 of this Embodiment 2 shown by FIG. 5, the 3-glycidoxy propyl triethoxysilane 13 which is an epoxy-type compound is used as a surface modifier. Numerous hydroxyl groups (—OH) are attached to the surface of the nano hollow particle 1 made of silica shell, and in FIG. 5, only three of the innumerable hydroxyl groups are shown so that the reaction can be easily understood.

  On the other hand, 3-glycidoxypropyltriethoxysilane 13 as a surface modifier is used in an autoclave with 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 enters a supercritical state, and freely enters between the nano hollow particles 1 made of silica shells aggregated as giant aggregated particles on the order of several μm to several tens of μm. All three ethoxy groups of 3-glycidoxypropyltriethoxysilane 13 undergo a condensation reaction with hydroxyl groups on the surface of nano hollow particles 1 made of silica shells, and bind to the surfaces of nano hollow particles 1 made of silica shells.

  In this way, by reacting innumerable hydroxyl groups on the surface of the nano hollow particle 1 made of silica shell and 3-glycidoxypropyltriethoxysilane 13, as shown in FIG. 5, the nano hollow made of silica shell is made. The surface of the particle 1 is covered with 3-glycidoxypropyltriethoxysilane 13 to form the dispersible silica nano hollow particle 8A according to the specific example 2 of the second embodiment.

 As a result, the nano hollow particles 1 composed of silica shells aggregated as giant aggregated particles on the order of several μm to several tens of μm are dispersed to form fine aggregated particles on the order of several hundreds of nm. In addition, the epoxy group reacts with the active group of the organic synthetic resin to form a strong bond with the organic synthetic resin, whereby the dispersible silica nano hollow particles 8A that are more easily uniformly dispersed in the organic synthetic resin are obtained. The dispersible silica nano hollow particles 8A are hydrophilic dispersible silica nano hollow particles.

  Further, as shown in FIG. 6, in specific example 3 of the second embodiment, methyltriethoxysilane 14 is used as a surface modifier. Numerous hydroxyl groups (—OH) are attached to the surface of the nano hollow particle 1 made of silica shell, and FIG. 6 shows only three of the innumerable hydroxyl groups so that the reaction can be easily understood.

  In contrast, methyltriethoxysilane 14 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 the nano hollow particles 1 composed of silica shells aggregated as giant aggregated particles on the order of several μm to several tens of μm. All three of the ethoxy groups are condensed with hydroxyl groups on the surface of the nano hollow particle 1 made of silica shell, and bonded to the surface of the nano hollow particle 1 made of silica shell.

  In this way, by reacting innumerable hydroxyl groups on the surface of the nano hollow particle 1 made of silica shell and methyltriethoxysilane 14, the surface of the nano hollow particle 1 made of silica shell becomes as shown in FIG. 6. Covered with methyltriethoxysilane 14, dispersible silica nano hollow particles 8 </ b> B according to Specific Example 3 of Embodiment 2 are formed.

 As a result, the nano hollow particles 1 composed of silica shells aggregated as giant aggregated particles on the order of several μm to several tens of μm are dispersed to form fine aggregated particles on the order of several hundreds of nm. In addition, when the methyl group reacts with the active group of the organic synthetic resin to form a strong bond with the organic synthetic resin, the dispersible silica nano hollow particles 8B that are more easily uniformly dispersed in the organic synthetic resin are obtained. The dispersible silica nano hollow particles 8B are lipophilic dispersible silica nano hollow particles.

  Furthermore, as shown in FIG. 7, in the fourth specific example of the second embodiment, acryloxypropyltrimethoxysilane 15 is used as the surface modifier. Numerous hydroxyl groups (—OH) are attached to the surface of the nano hollow particle 1 made of silica shell, and FIG. 7 shows only three of the innumerable hydroxyl groups so that the reaction can be easily understood.

  On the other hand, acryloxypropyltrimethoxysilane 15 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 becomes a supercritical state, and freely enters between the nano hollow particles 1 composed of silica shells aggregated as giant aggregated particles on the order of several μm to several tens of μm. All three of the methoxy groups of the trimethoxysilane 15 undergo a condensation reaction with the hydroxyl groups on the surface of the nano hollow particles 1 made of silica shells, and bind to the surfaces of the nano hollow particles 1 made of silica shells.

  In this way, by reacting innumerable hydroxyl groups on the surface of the nano hollow particle 1 made of silica shell and acryloxypropyltrimethoxysilane 15, as shown in FIG. 7, the nano hollow particle 1 made of silica shell 1 The surface is covered with acryloxypropyltrimethoxysilane 15 to form dispersible silica nano-hollow particles 8C according to Specific Example 4 of Embodiment 2.

 As a result, the nano hollow particles 1 composed of silica shells aggregated as giant aggregated particles on the order of several μm to several tens of μm are dispersed to form fine aggregated particles on the order of several hundreds of nm. Instead, the acryloxy group reacts with the active group of the organic synthetic resin to form a strong bond with the organic synthetic resin, so that the dispersible silica nano hollow particles 8C that are more easily uniformly dispersed in the organic synthetic resin are obtained. In addition, since the acryloxy group is a UV functional group that reacts with ultraviolet rays (UV), dispersibility that cures in response to ultraviolet rays can be obtained by using the dispersible silica nano hollow particles 8C according to the specific example 4 of Embodiment 2. The silica nano hollow particles 8C can be applied to various uses.

  As shown in FIG. 3, after the powdery dispersible silica nano hollow particles 8, 8A, 8B, and 8C produced in this way are mixed well with the pellet-shaped organic synthetic resin 6 in advance in a dry state, Heat kneading is performed in the kneader (step S26). The melted organic synthetic resin 6 and the dispersible silica nano hollow particles 8, 8A, 8B, 8C are kneaded so as to be sufficiently uniform by a kneader, and then extruded by an extruder (step S27). The mixture extruded from the machine die is pelletized (step S28).

  The pelletizing method is divided into two types, strand cut and hot cut, as in the first embodiment. In this way, the hollow silica particles according to the second embodiment, in which the dispersible silica nano hollow particles 8, 8A, 8B, 8C are contained in the organic synthetic resin 6 within the range of 20 wt% to 40 wt%. Master batch 10A is manufactured.

  In Example 2 of the second embodiment, triethoxypropyl isocyanate silane (TEIS) 12 is used as the surface modifier, and polypropylene (PP) is used as the organic synthetic resin 6, and the manufacturing process shown in FIG. Accordingly, a hollow particle-containing master batch 10A containing the dispersible silica nano hollow particles 8 at a high concentration of 30% by weight was produced. In addition, in the pelletization of step S28 of FIG. 3, since a polypropylene is hard to become a rod shape rather than a polyethylene, it was made into a rice grain-shaped pellet by hot cutting.

  The hollow particle-containing master batch 10A contains the dispersible silica nano hollow particles 8 at a high concentration of 30% by weight. A surface layer of polypropylene containing 5 to 6% by weight of dispersible silica nano hollow particles 8 is formed on the surface of a normal plastic molding by molding or two-stage molding, or dispersible silica nano is formed by calender molding. A polypropylene film containing the hollow particles 8 at a ratio of 5 to 6% by weight can be formed.

  In such a product, since the dispersible silica nano hollow particles 8 are uniformly dispersed in the polypropylene, the silica nano hollow particles 1 exhibit remarkable properties such as heat insulating properties, transparency, high dielectric constant, and the like. -It can be suitably used for applications requiring properties such as transparency and high dielectric constant. And by supplying as hollow particle containing masterbatch 10A, content of the dispersible silica nano hollow particle 8 in a product can be set freely and correctly.

 In this way, in the hollow particle-containing master batch 10A according to the second embodiment, the silica nano hollow particles 1 are prevented from agglomerating and dispersed as fine agglomerated particles in polypropylene 6 as an organic synthetic resin, and are solid. By modifying the surface so that a larger amount can be mixed, the application field of the silica nano hollow particles 1 can be further expanded and the use can be facilitated.

  In each of the above-described embodiments, the hollow silica particles having a silica shell having an outer diameter in the range of about 50 nm to 100 nm and an average outer diameter of 70 nm and a porosity of about 70% to 80% are used. Although the case where the nano hollow particle 1 made of a shell is used has been described, any nano hollow particle made of a silica shell having an outer diameter of about 30 nm to about 300 nm may be used.

  In each of the above embodiments, only the case where ethanol or n-hexane is used as the organic solvent for surface modification has been described. However, the present invention is not limited to this, and other organic solvents such as methanol, propanol, etc. Aliphatic alcohols, aromatic hydrocarbons such as xylene, and the like can be used.

 Furthermore, although only the case where monoamine modified silicone oil and triethoxypropyl isocyanate silane (TEIS) were used as a surface modifier was described, it is not limited to this, and other surface modifiers such as modified silicone oil, Modified silicone oil introduced with hydrophilic organic groups such as polyether group, ethoxy group, carboxyl group, modified silicone oil introduced with lipophilic organic groups such as amino group, alkyl group, etc. may be used. 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, and the like may be used.

  In carrying out the present invention, the configuration, components, shape, quantity, material, size, manufacturing method, and the like of the other parts of the hollow particle-containing masterbatch are not limited to the above embodiments.

  In addition, since the numerical value quoted in each embodiment of the present invention does not indicate a critical value but indicates a preferable value suitable for implementation, even if the numerical value is slightly changed, the implementation is denied. It is not a thing.

FIG. 1 is a schematic diagram showing a process for producing nano hollow particles made of silica shells used for producing a hollow particle-containing master batch according to Embodiment 1 of the present invention. FIG. 2 is a flowchart showing a method for manufacturing a hollow particle-containing masterbatch according to Embodiment 1 of the present invention. FIG. 3 is a flowchart showing a method for manufacturing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention. FIG. 4 is a schematic diagram showing a specific example 1 of the surface modification method in the method for producing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention. FIG. 5 is a schematic diagram showing a specific example 2 of the surface modification method in the method for producing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention. FIG. 6 is a schematic diagram showing a specific example 3 of the surface modification method in the method for producing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention. FIG. 7 is a schematic diagram showing a specific example 4 of the surface modification method in the method for producing a hollow particle-containing masterbatch according to Embodiment 2 of the present invention.

Explanation of symbols

1 Nano hollow particles made of silica shell 2 Core particles (calcium carbonate)
3 Silica coating 5, 8, 8A, 8B, 8C Dispersible silica nano hollow particles 6 Organic synthetic resin 10, 10A Hollow particle containing master batch 12, 13, 14, 15 Surface modifier

Claims (4)

A master batch formed by forming nano hollow particles made of silica shells having an outer diameter in a range of about 30 nm to about 300 nm into an organic synthetic resin and uniformly forming them into a pellet shape,
Dispersible silica nano hollow particles obtained by surface-modifying a nano hollow particle composed of silica shell by reaction addition are included in the organic synthetic resin within a range of 20 wt% to 40 wt%. A hollow particle-containing masterbatch characterized by   The dispersible silica nano-hollow particles are prepared by adding an organic solvent and the surface modifier to the nano-hollow particles made of the silica shell and dispersing the nano-particles made of the silica shell strongly with a wet jet mill. The hollow particle-containing masterbatch according to claim 1, wherein the surface modification is carried out by reaction addition.   The surface modification is performed by adding the organic solvent and the surface modifier to the hollow nanoparticle composed of the silica shell to produce a mixture, and applying high temperature and high pressure to the mixture to obtain a supercritical state of the organic solvent, whereby the silica shell The hollow particle-containing masterbatch according to claim 2, wherein the surface modifier is reacted and added to the surface of the nano hollow particles comprising:   The said organic synthetic resin is polyethylene or a polypropylene, The hollow particle containing masterbatch as described in any one of Claim 1 thru | or 3 characterized by the above-mentioned.

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