JP6679043B2 - Nano composite - Google Patents

Description

  The present invention relates to a nanocomposite, a nanocomposite dispersion, a composite material, a coating agent, a method for producing a nanocomposite, a method for producing a nanocomposite dispersion, and a method for producing a composite material.

  Heat generation from electronic components is becoming more serious as electronic equipment and communication equipment become smaller, the amount of signals handled increases, and processing speed increases, leading to the development of resin components with high heat dissipation. Has been.

  On the other hand, resin members which are excellent in moldability and have a high degree of freedom in design are also used in the field of automobiles. Due to the miniaturization and improved performance of automobile products, measures against heat generation, which have not been emphasized until now, have been reviewed, and the demand for higher thermal conductivity is increasing.

  Further, in recent years, the demand for LED lighting has been increasing due to an increase in environmental awareness. In order to improve the luminous efficiency of LEDs, heat dissipation technology is important, and aluminum heat sinks and the like have been used conventionally, but development of heat conductive resin is also actively carried out from the viewpoint of weight reduction and the like. . In addition, it is also important to transmit light in the LED lighting and members around the display.

In order to obtain an efficient heat dissipation effect of a resin, it is generally performed to add an inorganic powder such as an oxide as a filler to obtain a high thermal conductivity.
Magnesium oxide has the highest thermal conductivity, good insulating properties, relatively low hardness, and low cost among practical oxide ceramics, so it is expected as an application material for heat dissipation fillers. Has been done. However, magnesium oxide is limited in its application range as a heat radiation filler due to its poor water resistance.

In order to solve the above problems, in Patent Document 1, a layer is formed on the surface of magnesium oxide to improve water resistance.
Further, in Patent Document 2, a predetermined amount of magnesium oxide fine particles are dispersed in a predetermined monohydric alcohol, and the D _{50 of the} magnesium oxide fine particles measured by a dynamic light scattering method is in the range of ₅ to 90 nm. And a magnesium oxide fine particle dispersion having a water content of 9000 mass ppm or less is described.

  On the other hand, as a material excellent in water-repellent / oil-repellent effect and hydrophilic / oil-repellent effect, Patent Document 3 discloses a specific compound containing a fluorine-containing terminal chain group and a specific amphiphilic group in the main chain skeleton. Nanomaterials and nanocomposites containing fluorine compounds have been disclosed.

JP, 2009-215134, A JP, 2014-114178, A JP, 2010-138156, A

However, in the manufacturing method described in Patent Document 1, although the crystallization is performed in the heating step, the heating temperature at this time is as high as around 1500 ° C. Since it can be easily estimated that it is difficult to maintain the particle shape and size of nano-sized fine particles due to sintering due to high temperature heating, it is difficult to apply this production method to nanoparticles.
In addition, the magnesium oxide fine particle dispersion liquid of Patent Document 2 is thickened only by the inclusion of ppm-order water, and is not suitable for use in an aqueous system or for use in which water may be incorporated.
As described above, there is still a shortage of techniques for improving the water resistance of magnesium oxide fine particles whose particle size is controlled to the nano size.

  The present invention has good resistance to external influences such as water resistance and acid resistance, can effectively exhibit the excellent thermal conductivity inherent in magnesium oxide nanoparticles, and can be dispersed in a liquid dispersion medium or an organic material. Provided is a nanocomposite containing magnesium oxide nanoparticles having excellent properties.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide magnesium oxide nanoparticles to which resistance such as high water resistance and acid resistance is imparted. In addition, it is an object of the present invention to provide a nanocomposite that exhibits high dispersibility in a liquid and can be used as an additive or coating agent that imparts water and oil repellency, and a dispersion thereof.

  The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and have a fluorine group at both ends, and a specific fluorine-containing oligomer having an alkoxysilyl group in the main chain skeleton is used. It was found that the nanocomposite is formed by reacting the above under alkaline condition. Furthermore, this composite is nano-sized fine particles, and in addition to the extremely high water resistance not found in conventional magnesium oxide nanoparticles, the surface of the fine particles also exhibits high water and oil repellency. High affinity for general-purpose organic solvents following the lyophilic property, it was found that these nanoparticles can be easily dispersed in a desired liquid, and that the substrate surface can be modified with this dispersion, The present invention has been completed based on these findings.

The present invention has solved the above problems by the following technical configurations.
(I) A nanocomposite containing a fluorine-containing oligomer represented by the following general formula (1) and / or a polymer thereof and magnesium oxide nanoparticles.

[In the above formula (1),
R ¹ , R ² , X and Y may be the same or different and each has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Indicates an alkylcarbonyloxy group.
R ^f1 and R ^{f2, which} may be the same or different, each represent (CF ₂ ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F ₇ . (Wherein ^{X 1} represents a hydrogen atom, a fluorine atom, or chlorine atom, _{n 2} is a number of 1 to 10, _{n 3} is a number of 0-8.)
n ₁ is a number of 1 to 3, _{m 1} is the number of 1 to 10, _{m 2} represents a number of 0. ]

(II) The nanocomposite according to (I) above, wherein the fluorinated oligomer is a compound represented by the following general formula (1-1).

In General Formula ^{(1-1), R f3} and ^{R f4} are _{each, - (CF 2) p F} , and _{-CF (CF 3) O (CF} 2 CFCF 3 O) q C 3 F 7 (p is A group of 1 to 10 and q is a number of 0 to 5). o is a number from 1 to 10. ]

(III) The nanocomposite according to (I) or (II), wherein the polymer having the fluorine-containing oligomer as a constituent unit is complexed with magnesium oxide nanoparticles, and the average particle size is 5 to 500 nm.

(IV) The nanocomposite according to any one of (I) to (III), wherein the ratio of the fluorinated oligomer with respect to 100 parts by mass of the magnesium oxide nanoparticles is 5 to 400 parts by mass.

(V) A nanocomposite dispersion liquid obtained by dispersing the nanocomposite according to any one of (I) to (IV) in a dispersion medium.

(VI) A composite material obtained by dispersing the nanocomposite according to any one of (I) to (IV) or the nanocomposite dispersion according to (V) in an organic material.

(VII) The organic material is selected from resins, polymerizable monomers and polymerizable oligomers 1
The composite material according to (VI) above, which is one or more kinds of organic materials.

(VIII) A coating agent comprising the nanocomposite dispersion described in (V).

(IX) mixing the fluorine-containing oligomer represented by the general formula (1), magnesium oxide nanoparticles and a dispersion medium to obtain a mixed liquid,
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
Removing the dispersion medium from the dispersion,
A method for producing a nanocomposite, comprising:

(X) mixing the fluorine-containing oligomer represented by the general formula (1), the magnesium oxide nanoparticles, and the first dispersion medium to obtain a mixed liquid,
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
Removing the first dispersion medium from the dispersion to obtain a nanocomposite;
Dispersing the nanocomposite in a second dispersion medium,
A method for producing a nanocomposite dispersion, comprising:

(XI) a step of mixing the fluorine-containing oligomer represented by the general formula (1), the magnesium oxide nanoparticles, and the first dispersion medium to obtain a mixed liquid,
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
A method for producing a nanocomposite dispersion, comprising:

(XII) The nanocomposite according to any one of (I) to (IV) or the above (V)
A method for producing a composite material, which comprises the step of dispersing the nanocomposite dispersion liquid according to 1. into an organic material.

  INDUSTRIAL APPLICABILITY The nanocomposite of the present invention not only imparts high water resistance to the magnesium oxide nanoparticles, but due to the effect of fluorine, the nanocomposite or its dispersion shows high dispersibility in a liquid and is water repellent. -It can be used as an additive or coating agent that imparts oil repellency.

5 is a field emission scanning electron microscope (FE-SEM) image photograph of untreated magnesium oxide nanoparticles and the nanocomposite of Example 4. 2 is an X-ray diffraction (XRD) pattern of untreated magnesium oxide nanoparticles before and after the water resistance test and the nanocomposites of Examples 1 and 4. 3 is an X-ray diffraction (XRD) pattern of untreated magnesium oxide nanoparticles after the acid resistance test and the nanocomposites of Examples 1 and 4. 5 is a chart of untreated magnesium oxide nanoparticles and a thermogravimetric analyzer (TGA) of Examples 1 to 4. 3 is an XRD pattern of the nanocomposite of Example 1 after heat treatment.

  Hereinafter, the nanocomposite of the present invention, a dispersion thereof, a composite material containing the nanocomposite, a coating agent containing the dispersion, and a method for producing these will be described.

[Nanocomposite]
The nanocomposite of the present invention is a composite including a fluorine-containing oligomer represented by the following general formula (1) (hereinafter referred to as fluorine-containing oligomer (1)) and magnesium oxide nanoparticles. This composite is a nano-sized composite particle.

[In the above formula (1),
R ¹ , R ² , X and Y may be the same or different and each has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Indicates an alkylcarbonyloxy group.
R ^f1 and R ^{f2, which} may be the same or different, each represent (CF ₂ ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F ₇ . (Wherein ^{X 1} represents a hydrogen atom, a fluorine atom, or chlorine atom, _{n 2} is a number of 1 to 10, _{n 3} is a number of 0-8.)
n ₁ is a number of 1 to 3, _{m 1} is the number of 1 to 10, _{m 2} represents a number of 0. ]

In general formula (1), R ¹ and R ² are each preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group or an ethyl group.
In general formula (1), each of X and Y is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably a methoxy group or an ethoxy group.
In general formula (1), m ₁ is preferably a number of ₁ to 7, and more preferably 2 to 3.
In general formula (1), m ₂ is preferably a number from 0 to 5, and more preferably 0.
In the general formula (1), R ^f1 and R ^f2 are perfluoro represented by (CF ₂ ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F _7. It is an alkyl group, and examples thereof include C ₃ F ₇ , C ₆ F ₁₃ , and C ₇ F ₁₅ . ^As examples of perfluoroalkyl oxaalkyl group ^{R f1} and ^{R f2} _{are, -CF (CF 3) OC 3} F 7 and the like.
R ^f1 and R ^{f2 at} both ends may be the same or different from each other, and R ^f1 and R ^f2 may be different from each other between molecules.
X ¹ is preferably a fluorine atom.
In the general formula (1), n ₁ is a number of ₁ to 3.
In general formula (1), n ₂ is preferably a number of 3 to 7.
In general formula (1), n ₃ is preferably a number of 0 to 3.
The number may be an integer.

  The fluorine-containing oligomer (1) is preferably a compound represented by the following general formula (1-1).

In General Formula ^{(1-1), R f3} and ^{R f4} are _{each, - (CF 2) p F} , and _{-CF (CF 3) O (CF} 2 CFCF 3 O) q C 3 F 7 (p is A group of 1 to 10 and q is a number of 0 to 5). o is a number from 1 to 10. ]

In the general formula ^{(1-1), R f3} and ^{R f4} are _{each, -CF (CF 3) O (} CF 2 CFCF 3 O) q C 3 F 7 is preferred. Moreover, p is preferably a number of 3 to 6. Further, q is preferably a number of 0 to 3. o is preferably 2 to 5, more preferably 2 to 3.

  The magnesium oxide nanoparticles are magnesium oxide particles whose particle size is controlled to nano size. The magnesium oxide nanoparticles are not particularly limited, but in order to obtain the fluorine-containing nanocomposite, dispersion, and composite material of the present invention, the magnesium oxide nanoparticles have an average particle diameter of 5 to 500 nm, and further 10 to 50 nm. Is preferred. This average particle diameter is measured by a dynamic light scattering method (DLS: Dynamic Light Scattering Measurement). The average particle diameter can be measured, for example, by a dynamic light scattering photometer, and specifically, magnesium oxide nanoparticles are stirred and dispersed in a dispersion medium for about 24 hours with a magnetic stirrer, and the obtained dispersion liquid is obtained. It can be measured using a dynamic light scattering photometer (for example, Otsuka Electronics Co., Ltd., model number: DLS-7000HL).

  The nanocomposite of the present invention is preferably a composite of a polymer having the fluorinated oligomer (1) as a constituent unit and magnesium oxide nanoparticles. Further, the nanocomposite of the present invention has a core-shell structure in which a polymer having a fluorine-containing oligomer (1) as a constituent unit is a shell and magnesium oxide nanoparticles are a core, for example, a fluorine-containing oligomer (1). It is preferable that the shell of the polymer having a structural unit of 10 is a capsule in which the magnesium oxide nanoparticles as the core are encapsulated.

  The nanocomposite of the present invention is obtained by subjecting the magnesium oxide nanoparticles and the fluorinated oligomer (1) to a sol-gel reaction under acidic or alkaline conditions, preferably alkaline conditions. In this reaction, it is considered that the polymer containing the fluorine-containing oligomer (1) as a constitutional unit becomes a gelled product, and that a network structure (matrix) composed of SiO is present. In other words, it is considered that the nanocomposite of the present invention has magnesium oxide nanoparticles as a core and the magnesium oxide nanoparticles are encapsulated by the network structure described above. In addition, in some of the fluorine-containing oligomer (1), the alkoxysilyl group may react with the hydroxyl group slightly present on the surface of magnesium oxide.

The present invention includes a nanocomposite obtained by reacting the fluorinated oligomer (1) with magnesium oxide nanoparticles.
The present invention includes a nanocomposite obtained by reacting the fluorinated oligomer (1) in the presence of magnesium oxide nanoparticles.
The present invention includes a nanocomposite in which a polymer of the fluorinated oligomer (1) and magnesium oxide nanoparticles are combined.

  The nanocomposite of the present invention is in the form of particles, and the individual particles are not particularly limited in shape, but are preferably spherical or nearly spherical. The average particle size of the nanocomposite of the present invention is preferably 5 to 500 nm, more preferably 20 to 100 nm, still more preferably 20 to 70 nm. This is because if it is less than 5 nm, the primary particles will agglomerate and handling will be difficult. On the other hand, when it exceeds 500 nm, mechanical properties may be deteriorated when compounded in a resin film or a resin molded product. In addition, there is concern that the transparency of the resin film may be impaired. The average particle diameter of the nanocomposite of the present invention is measured by a dynamic light scattering method (DLS). The average particle diameter can be measured, for example, by a dynamic light scattering photometer. Specifically, the nanocomposite is stirred and dispersed in a dispersion medium for about 24 hours with a magnetic stirrer, and the obtained dispersion liquid is subjected to dynamic light scattering. It can be measured using a scattering photometer (for example, model number: DLS-7000HL, manufactured by Otsuka Electronics Co., Ltd.).

  In the nanocomposite of the present invention, the ratio of the fluorinated oligomer (1) and / or the polymer thereof to 100 parts by mass of the magnesium oxide nanoparticles is preferably 5 to 400 parts by mass, more preferably 10 to 200 parts by mass, and 20 to 20 parts by mass. More preferably 100 parts by mass.

[Nanocomposite manufacturing method]
The production method of the nanocomposite of the present invention is shown below, but the production method is not limited to this.
The nanocomposite of the present invention can be produced by reacting the fluorinated oligomer (1) with magnesium oxide nanoparticles.

The method for producing the nanocomposite of the present invention includes:
Mixing the fluorine-containing oligomer represented by the general formula (1), magnesium oxide nanoparticles, and a dispersion medium to obtain a mixed liquid;
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
Removing the dispersion medium from the dispersion,
And a method for producing a nanocomposite (hereinafter referred to as production method 1).

  In the production method 1, the ratio of the fluorinated oligomer (1) to 100 parts by mass of the magnesium oxide nanoparticles is preferably 5 to 400 parts by mass, more preferably 10 to 200 parts by mass, still more preferably 20 to 100 parts by mass. If the ratio exceeds 400 parts by mass, the manufacturing cost may increase due to the material cost, and if it is less than 5 parts by mass, the water resistance and dispersibility of the magnesium oxide nanoparticles may decrease. This is because the organic material may not have sufficient surface properties (antifouling property, water repellency, oil repellency, etc.).

Examples of the dispersion medium include acetic acid esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as ethethyl ethyl cellosolve, alcohols such as methanol, 2-propanol, t-butanol, and n-butanol, 1,1,2,2,3,3,4-heptafluorocyclopentane [Example of commercially available product: Zeorora H (a cyclic fluorine solvent manufactured by Nippon Zeon Co., Ltd.)] or 3,3-dichloro-1,1, 1,2,2-Pentafluoropropane / 1,3-dichloro-1,1,2,2,3-pentafluoropropane mixture [Example of commercially available product: Asahi Klin AK225 (Asahi Glass Co., Ltd., fluorine solvent) ] And other fluorine-based solvents, water, and the like, but are not limited thereto.
The dispersion medium preferably contains an alcohol, especially a monohydric alcohol having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and a dispersion medium selected from water. When alcohol and water are used in combination, the mass% of water in the total dispersion medium is preferably 0.1 to 40, more preferably 0.1 to 30.

  In Production Method 1, it is preferable to adjust the amount and type of these so that the fluorinated oligomer (1), the magnesium oxide nanoparticles and the dispersion medium are mixed to obtain a mixed solution in a sol state.

  The production method 1 has a step of reacting the fluorine-containing oligomer with the magnesium oxide nanoparticles under the alkaline condition of the mixed solution obtained in the above step, preferably the mixed solution in a sol state to obtain a nanocomposite dispersion. The alkaline condition is obtained by adding an alkaline agent such as ammonia to the mixed solution. It is preferable to mix an aqueous solution of an alkaline agent. The alkaline conditions preferably have a pH of 8 to 14, more preferably 9 to 13. This pH may be the pH at the temperature of the reaction system when the fluorine-containing oligomer (1) is reacted with the magnesium oxide nanoparticles.

  The reaction temperature of the fluorine-containing oligomer and the magnesium oxide nanoparticles can be selected preferably from 0 to 60 ° C, more preferably from 10 to 40 ° C, depending on the kind and amount of the reaction raw material.

  The reaction time between the fluorine-containing oligomer and the magnesium oxide nanoparticles is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, further preferably 30 minutes to 5 hours, depending on the kind and amount of the reaction raw materials. You can choose from.

  The completion of the reaction between the fluorinated oligomer and the magnesium oxide nanoparticles can be confirmed by the occurrence of cloudiness or the precipitation of the precipitate. Upon completion of the reaction, a dispersion liquid of a nanocomposite containing the fluorine-containing oligomer (1) and / or its polymer and magnesium oxide nanoparticles is obtained.

  The production method 1 has a step of removing the dispersion medium from the dispersion liquid of the nanocomposite containing the fluorine-containing oligomer (1) and / or its polymer and magnesium oxide nanoparticles. For removing the dispersion medium, a known method can be adopted depending on the type and amount of the dispersion medium. For example, when the dispersion medium is an alcohol, and further a monohydric alcohol having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, it can be removed by vacuum distillation using an evaporator or the like. By removing the dispersion medium, a powdered nanocomposite is obtained.

[Nanocomposite dispersion and method for producing the same]
The present invention provides a nanocomposite dispersion obtained by dispersing the nanocomposite of the present invention in a dispersion medium.
The concentration of the nanocomposite in the nanocomposite dispersion can be selected from 5 to 10% by mass, further 10 to 20% by mass, and further 20 to 30% by mass, depending on the type of the nanocomposite and the use of the dispersion.
The dispersion medium of the nanocomposite dispersion liquid can be selected from the dispersion medium described in the production method 1.

  The nanocomposite dispersion of the present invention can be applied to a substrate and dried to form a film on the surface of the substrate. This coating has a large contact angle with an organic medium such as oleic acid and dodecane and exhibits oil repellency, and also has a large contact angle with water and exhibits antifouling properties. It can be used as a coating agent for oils and antifouling agents. Accordingly, the present invention provides a coating agent comprising the nanocomposite dispersion of the present invention.

  When applying the nanocomposite dispersion of the present invention, for example, a substrate (metal, glass, rubber, resin, cloth, wood, paper, etc.), the nanocomposite dispersion is applied by spraying, spin, dip, etc., A coating film is formed on the surface of the base material. The application may be such that the surface of the substrate is modified.

  The method for producing the nanocomposite dispersion of the present invention is shown below, but the present invention is not limited to this.

The nanocomposite dispersion of the present invention can be prepared by redispersing the nanocomposite obtained by the above production method 1 in a dispersion medium.
Further, the nanocomposite dispersion of the present invention can be prepared by adopting the steps up to the preceding step of the final step of removing the dispersion medium in the production method 1. That is, the nanocomposite dispersion can be produced by mixing and reacting a solution containing magnesium oxide nanoparticles in the presence of the fluorinated oligomer (1).

Specific examples of the method for producing the nanocomposite dispersion of the present invention include the following.
A step of mixing the fluorine-containing oligomer represented by the general formula (1), the magnesium oxide nanoparticles, and the first dispersion medium to obtain a mixed liquid;
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
Removing the first dispersion medium from the dispersion to obtain a nanocomposite;
Dispersing the nanocomposite in a second dispersion medium,
A method for producing a nanocomposite dispersion liquid containing: (hereinafter referred to as production method 2).

A step of mixing the fluorine-containing oligomer represented by the general formula (1), the magnesium oxide nanoparticles, and the first dispersion medium to obtain a mixed liquid;
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
A method for producing a nanocomposite dispersion liquid containing (hereinafter, referred to as production method 3).

In manufacturing methods 2 and 3, steps common to manufacturing method 1 can be performed in the same manner as manufacturing method 1. The first dispersion medium of production method 2 corresponds to the dispersion medium of production method 1.
In the manufacturing method 2, in the step of dispersing the nanocomposite in the second dispersion medium, the second dispersion medium may be of the same type as the first dispersion medium or of a different type. Each of the first and second dispersion media can be selected from the dispersion media described in the production method 1. In the manufacturing method 2, the second dispersion medium is preferably an alcohol, a monohydric alcohol having 1 to 6 carbon atoms, and a monohydric alcohol having 1 to 3 carbon atoms. In the production method 2, the second dispersion medium preferably has a low water content, for example, 5% by mass or less.

[Composite Material and Manufacturing Method Thereof]
The present invention provides a composite material obtained by dispersing the above nanocomposite of the present invention or the above nanocomposite dispersion of the present invention in an organic material. The composite material of the present invention contains the nanocomposite of the present invention.

  In the state of the composite material, the fluorinated oligomer (1) has a network structure in which the sol-gel reaction proceeds. This fluorine-containing oligomer (1) has high fluorine atoms (atoms that contribute to improvement of surface characteristics) at both ends, so that it is high on the surface of the finally obtained resin film or resin molded product. The fluorine atom can be efficiently present. As a result, the surface characteristics (antifouling property, water repellency, oil repellency, etc.) of the resin film and the resin molded product are improved.

  Examples of the organic material include one or more kinds of organic materials selected from resins, polymerizable monomers and polymerizable oligomers.

  Examples of the resin include phenol resin (PF), epoxy resin (EP), melamine resin (MF), urea resin (urea resin, UF), unsaturated polyester resin (UP), alkyd resin, polyurethane (PUR), and thermosetting. Thermosetting resin such as polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polyurethane (PUR), ABS resin (acrylonitrile butadiene styrene resin), thermoplastic resin such as acrylic resin (PMMA), polyamide (PA) nylon, polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE), polyethylene terephthalate (PET) , Grass phi -Engineering plastics such as reinforced polyethylene terephthalate (GF-PET), polybutylene terephthalate (PBT), cyclic polyolefin (COP), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polysulfone (PSF), polyether. Examples include super engineering plastics such as sulfone (PES), but are not limited thereto.

  As the polymerizable monomer and / or oligomer, a polyfunctional monomer and / or oligomer having two or more polymerizable functional groups (that is, bifunctional) is preferable. For example, trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate. , Dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) ) Acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin tetra (meth) acrylate, adamantyl di (Meth) acrylate, isobornyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and those modified with PO, EO, etc. Difunctional monomer, pentaerythritol triacrylate (PETA), neopentyl glycol diacrylate (NPGDA), dipentaerythritol hexaacrylate (DPHA), Pentaerythritol pentaacrylate (DPPA), polyfunctional monomers such as trimethylolpropane triacrylate (TMPTA), urethane oligomer other functional, there may be mentioned oligomers such as polyester oligomers, but not limited to.

  In addition, from the viewpoint of coating film hardness and the like, the above-mentioned bifunctional or higher functional monomer and / or bifunctional or higher functional oligomer is suitable, but for the purpose of adjusting viscosity, etc., a monofunctional monomer and / or a monofunctional functional oligomer is used. You can also

  The ratio of the nanocomposite to the organic material is preferably 0.01 to 1000 parts by mass, more preferably 0.05 to 800 parts by mass, and still more preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the organic material. Parts by mass. If it is less than 0.01 parts by mass, the thermal conductivity, water / oil repellency, chemical stability, acid resistance and surface properties of the obtained molded article cannot be sufficiently improved, and if it exceeds 1000 parts by mass. This is because the mechanical properties such as flexibility and elasticity of the obtained resin molded product may be deteriorated.

The production method of the composite material of the present invention is shown below, but the production method is not limited to this.
Examples of the method for producing the composite material of the present invention include a method for producing the composite material, which includes a step of dispersing the nanocomposite of the present invention or the nanocomposite dispersion liquid of the present invention in an organic material.

  For example, a resin dissolved in an organic solvent, a polymerizable monomer dissolved in an organic solvent, an oligomer dissolved in an organic solvent, or a pellet-like or powder-like resin containing no organic solvent or the like is added to the nanocomposite or nanocomposite of the present invention. After adding the dispersion liquid and coating it on a substrate, etc., in a state where a coating film is formed by heat curing or photocuring, or after the resin containing no organic solvent is heated and melted and mixed with the nanocomposite, the mold The composite material is obtained by forming the composite material into a predetermined shape.

  The surface modified by using the nanocomposite of the present invention exhibits water repellency and oil repellency, and exhibits excellent durability such as heat resistance, chemical resistance, and UV resistance, which are characteristics of fluorine. It is effective for applications that are often exposed to water and ultraviolet rays and are not easy to maintain, and applications where oils, fingerprints, cosmetics, sunscreen cream, human or animal excrement, oil, etc. are likely to adhere. , Window glass or tempered glass for ships, aircraft, skyscrapers, headlamp covers, outdoor products, telephone boxes, large outdoor displays, bathtubs, sanitary products such as wash basins, makeup tools, kitchen building materials, aquariums, Examples include coatings to prevent fingerprints from sticking to art objects. In addition, it is also useful as a fingerprint adhesion preventing coating for compact discs, DVDs, etc., as a mold release agent for paints, a paint additive, and a resin modifier. Also, medical equipment such as car navigation, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, gastrocameras, copiers, PCs. , Optical liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, antireflection films, and other optical products. Further, the nanocomposite of the present invention is excellent in water resistance of magnesium oxide and the like, and therefore, it is suitable as a filler and further as a filler for a semiconductor encapsulating resin.

  Hereinafter, the present invention will be described more specifically with reference to Examples. However, the nanocomposite, the nanocomposite dispersion and the method for producing the same according to the present invention are not limited to the following examples. The unit% represents mass% unless otherwise specified.

<Example 1>
At room temperature (25 ° C.), 200 mg of the fluorine-containing oligomer of the general formula (1-1) and 50 mg of magnesium oxide nanoparticles (average particle size: about 50 nm, Sigma-Aldrich Japan Co., Ltd.) were added to a sample bottle containing 5 ml of methanol. Addition was continued for 30 minutes or more. Furthermore, at room temperature (25 ° C.), 2 ml of 25% aqueous ammonia was added and the reaction was carried out for 5 hours. Here, the completion of the reaction can be confirmed by cloudiness or sedimentation of the precipitate. The obtained mixture was a dispersion [hereinafter, referred to as dispersion (A-1)] in which the nanocomposite of fluorine-containing oligomer / magnesium oxide nanoparticles was dispersed in methanol as a dispersion medium. The fluorine-containing oligomer was a compound in which R ^f3 and R ^f4 in the general formula (1-1) were each —CF (CF ₃ ) OC ₃ F ₇ , and o was 2 to 3.

  After completion of the reaction, methanol was removed from the dispersion liquid (A-1) using an evaporator (80 to 100 ° C.), and then the reaction product was again stirred and dispersed in methanol for several hours to be dispersed, and a centrifugal separator was further used. After removing methanol and washing with methanol three times, a precipitate was obtained. The obtained precipitate was vacuum dried at 50 ° C. for 24 hours to obtain a fluorine-containing oligomer / magnesium oxide nanocomposite as a powder. Table 1 shows the amount of the raw materials used, the yield of the nanocomposite, and the average particle size of the nanocomposite.

<Examples 2 to 4>
Nanocomposites were obtained according to the formulation shown in Table 1 below in accordance with Example 1. The results obtained are shown in Table 1. The nanocomposite dispersions obtained in the manufacturing process of Examples 2 to 4 were designated as dispersion (A-2), dispersion (A-3), and dispersion (A-4), respectively.

* 1 The number in parentheses of the amount used is the weight part of the fluorine-containing oligomer relative to 100 weight parts of the magnesium oxide nanoparticles (the same applies to Table 2).
* 2 The yield (%) of nanocomposite was derived from the following formula.
Yield of nanocomposite (%) = X / (Y + Z) × 100
X: Yield of nanocomposite
Y: Amount of fluorine-containing oligomer charged
Z: Charge amount of magnesium oxide nanoparticles * 3 The average particle size was measured by a dynamic light scattering method (DLS: manufactured by Otsuka Electronics Co., Ltd., model number: DLS-7000HL).

  The following methods evaluated the dispersibility, water resistance, acid resistance, and thermal decomposition behavior of the nanocomposites obtained in Examples 1 to 4. As a comparative example, untreated magnesium oxide nanoparticles were also evaluated.

[Nanocomposite dispersibility]
The dispersibility of the nanocomposite obtained in Example 4 was evaluated as follows.
A dispersion liquid prepared by dispersing magnesium oxide nanoparticles (untreated / the same as in Example 1) in methanol, and a dispersion liquid prepared by dispersing the fluorine-containing oligomer / magnesium oxide nanocomposite of Example 4 in methanol. The two types were evaluated by observing the state of the particles with an FE-SEM (Field Emission Scanning Electron Microscope) (manufactured by JEOL Ltd., model number: JSM-7000F). The results are shown in Fig. 1.

FIG. 1A is a FE-SEM photograph of a dispersion liquid of untreated magnesium oxide nanoparticles as a comparative example.
FIG. 1B is a FE-SEM photograph of the fluorine-containing oligomer / magnesium oxide nanocomposite of Example 4.
As shown in FIG. 1A (comparative example), the magnesium oxide nanoparticles alone cannot disperse the primary particles. On the other hand, the nanocomposite of Example 4 could be monodispersed in methanol (see FIG. 1 (B)).
As described above, this is because the fluorine-containing oligomer in which fluorine atoms are introduced at both ends forms a molecular assembly and functions as a so-called dispersant, and after the magnesium oxide nanoparticles are dispersed to the primary particles, It shows that the fluorinated oligomer and the magnesium oxide nanoparticles are combined.

[Water resistance of nanocomposite]
The water resistance of the nanocomposites obtained in Examples 1 and 4 was evaluated as follows.
10 mg of untreated magnesium oxide nanoparticles and an amount of the nanocomposites of Examples 1 and 4 corresponding to a magnesium oxide content of 10 mg calculated from a thermogravimetric analyzer (TGA) were respectively immersed in water (5 ml) to magnetically The mixture was stirred and dispersed with a stirrer for a predetermined time. After that, water was removed by centrifugation and washing was performed twice with methanol. After vacuum drying at 50 ° C. for 1 day, the obtained powder was evaluated using XRD (X-ray diffraction) (manufactured by Rigaku Corporation, model number: MiniFlex600). Stirring was performed every 20 hours from the start of immersion for 120 hours, powder was obtained at each time, and the XRD pattern was measured. The results are shown in FIG. The thermogravimetric analyzer used was model number TG-DTA2000SA manufactured by Bruker AXS KK.

FIG. 2A is an XRD pattern of untreated magnesium oxide nanoparticles as a comparative example.
FIG. 2B is an XRD pattern of the fluorine-containing oligomer / magnesium oxide nanocomposite of Example 1.
FIG. 2C is an XRD pattern of the fluorine-containing oligomer / magnesium oxide nanocomposite of Example 4.
As shown in FIG. 2 (A) (comparative example), the untreated magnesium oxide nanoparticles have a magnesium hydroxide pattern formed by immersion in water for 20 hours, while FIG. As shown in FIG. 2 (C), the nanocomposites of Examples 1 and 4 did not have a magnesium hydroxide pattern even after 120 hours of immersion in water, and could maintain the magnesium oxide crystal structure. I understand.

[Nanocomposite acid resistance]
The acid resistance of the nanocomposites obtained in Examples 1 and 4 was evaluated as follows.
10 mg of untreated magnesium oxide nanoparticles and an amount of the nanocomposites of Examples 1 and 4 corresponding to a magnesium oxide content of 10 mg calculated from a thermogravimetric analyzer (TGA) were each added to a 0.5 mM hydrochloric acid solution (1 ml). It was soaked for 48 hours. Then, the solution was removed by decantation. After drying at 100 ° C. for 1 day, the obtained powder was evaluated using XRD (X-ray diffraction) (manufactured by Rigaku Corporation, model number: MiniFlex 600). However, since the untreated magnesium oxide was completely dissolved in the solution, the solvent was removed at 100 ° C. and the powder was precipitated by drying for one day. The results are shown in Fig. 3. The thermogravimetric analyzer used was model number TG-DTA2000SA manufactured by Bruker AXS KK.

  From the results of XRD shown in FIG. 3, the untreated magnesium oxide nanoparticles had a magnesium chloride pattern after being immersed in hydrochloric acid for 48 hours, whereas the nanocomposites of Examples 1 and 4 were It can be seen that the magnesium pattern is not generated and the crystal structure of magnesium oxide can be maintained.

[Pyrolysis behavior of nanocomposites]
Regarding the thermal decomposition behavior of the fluorine-containing oligomer / magnesium oxide nanocomposites obtained in Examples 1 to 4, using a thermogravimetric analyzer (TGA), in an air atmosphere, at a temperature rising rate of 10 ° C / min, from room temperature to 800 ° C. Was measured up to. As the thermogravimetric analyzer, model number: TG-DTA2000SA manufactured by Bruker AXS KK was used. FIG. 3 shows the obtained results. In FIG. 3, the comparative example is the result for untreated magnesium oxide nanoparticles.

  From the results of TGA shown in FIG. 3, it can be confirmed that the degree of decrease in mass when the temperature exceeds 300 ° C. increases as the ratio of the fluorine-containing oligomer to the magnesium oxide nanoparticles increases.

Among the powders after the heat treatment at 800 ° C., the fluorine-containing oligomer / magnesium oxide nanocomposite of Example 1 was evaluated by XRD. FIG. 4 shows the results.
As shown in FIG. 4, a peak that was not observed before the heat treatment and was considered to be derived from MgF ₂ was observed together with the peak of MgO. From these results, it is shown that the present nanocomposite does not release harmful HF generated when a fluorine compound is thermally decomposed, that is, magnesium oxide can trap fluorine by forming a stable Mg-F bond. There is.

<Examples 5 to 8>
[Coating agent consisting of nanocomposite dispersion]
When preparing the nanocomposites of Examples 1 to 4, before the treatment with the evaporator, that is, without removing the dispersion medium, the nanocomposite dispersions can be used as they are as a coating agent. Using the nanocomposite dispersions in Examples 1 to 4, Examples 5 to 8 will specifically describe coating agents made of the nanocomposite dispersions.

[Example 5]
A slide glass (76 mm × 26 mm) degreased with ethanol was immersed in the dispersion liquid (A-1) prepared in Example 1 and then vacuum dried at 50 ° C. for 1 day to obtain a modified film. The contact angle of the obtained modified surface with water and dodecane was measured. The contact angle was measured with a contact angle measuring device (Kyowa Interface Science Co., Ltd., model number: DropMaster-301 (DM-301)). The obtained results are shown in Table 2.

[Examples 6 to 8]
In Example 6, the dispersion (A-2) prepared in Example 2, in Example 7 the dispersion (A-3) prepared in Example 3, and in Example 8 the dispersion prepared in Example 4 Using (A-4), according to Example 5, a modified slide glass was obtained. The obtained results are shown in Table 2.

  As shown in Table 2, the surface modified by the nanocomposite of the present invention exhibited super water / oil repellency. In particular, in Examples 5 and 6 in which the content of the fluorine-containing oligomer was high, the oil contact angle value was 100 ° or more, which was super oil repellency. It is considered that this is because the unreacted fluorine-containing oligomer lowers the surface energy and further enhances the oil repellency, in addition to the surface unevenness effect formed by the nanocomposite, the so-called Lotus effect.

<Examples 9 to 12>
[Composite material containing nanocomposite]
The composite material (modified PMMA film) of the nanocomposite and polymethylmethacrylate obtained in Examples 1 to 4 was prepared by the following method.
To a solution prepared by dissolving 990 mg of polymethylmethacrylate (PMMA) in about 50 g of THF (tetrahydrofuran), 10 mg of the fluorine-containing oligomer / magnesium oxide nanocomposite prepared in Examples 1 to 4 was added and dispersed. The obtained polymer solution was poured into a petri dish (made of glass), and then THF was vaporized and removed at room temperature (about 20 ° C.) to remove a polymer film, that is, a modified PMMA film composited with a nanocomposite. Got The contact angles of water and dodecane on the surface (the surface that was not in contact with the dish) and the back surface (the surface that was in contact with the dish) of the obtained modified film were measured. The contact angle was measured with a contact angle measuring device (Kyowa Interface Science Co., Ltd., model number: DropMaster-301 (DM-301)). Table 3 shows the obtained results.

The nanocomposite content in the modified PMMA films of Examples 9-12 is 1%.
As shown in Table 3, the film modified with the nanocomposite of the present invention showed higher water repellency and oil repellency on the surface than on the back surface of the film. Regular plastics exhibit lipophilicity. That is, it is understood that the back surface has the same performance as that of the conventional plastic (dodecane: 0 °), while the oil repellency due to fluorine can be imparted only to the front surface. In other words, in the solution state, the nanocomposite is uniformly dispersed in the solvent, but when preparing the PMMA film modified by the above method, the process of removing the solvent in the petri dish from the solution in which the nanocomposite is dispersed. Therefore, it can be estimated that the nanocomposite moves near the film surface.

Claims (15)

A nanocomposite comprising a fluorine-containing oligomer represented by the following general formula (1) and / or a polymer thereof and magnesium oxide nanoparticles.

[In the above formula (1),
R ¹ , R ² , X and Y may be the same or different and each has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Indicates an alkylcarbonyloxy group.
R ^f1 and R ^{f2, which} may be the same or different, each represent (CF ₂ ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F ₇ . (Wherein ^{X 1} represents a hydrogen atom, a fluorine atom, or chlorine atom, n2 the number of 1 to 10, n3 is a number of 0-8.)
n1 shows the number of 1-3, m1 shows the number of 1-10, and m2 shows the number of 0-10. ] The nanocomposite according to claim 1, wherein the fluorinated oligomer is a compound represented by the following general formula (1-1).

In General Formula ^{(1-1), R f3} and ^{R f4} are _{each, - (CF 2) p F} , and _{-CF (CF 3) O (CF} 2 CFCF 3 O) q C 3 F 7 (p is A group of 1 to 10 and q is a number of 0 to 5). o is a number from 1 to 10. ]   The nanocomposite according to claim 1 or 2, wherein the polymer having the fluorinated oligomer as a constituent unit is complexed with magnesium oxide nanoparticles, and the average particle size is 5 to 500 nm. The nanocomposite according to any one of claims 1 to 3 , which has a core-shell structure in which a polymer having a fluorine-containing oligomer as a structural unit is a shell and magnesium oxide nanoparticles are a core . It said ratio of the fluorine-containing oligomers and / or polymers thereof for 100 parts by weight of magnesium oxide nanoparticles, is 5 to 400 parts by weight, nanocomposite according to any one of claims 1-4. Nanocomposite dispersion comprising the nanocomposite is dispersed in a dispersion medium according to any one of claims 1-5. The nanocomposite dispersion according to nanocomposite or claim 6 according to any one of claims 1 to 5 is dispersed in an organic material, composite material. The composite material according to claim 7 , wherein the organic material is at least one organic material selected from a resin, a polymerizable monomer, and a polymerizable oligomer. A coating agent comprising the nanocomposite dispersion according to claim 6 . A step of mixing a fluorine-containing oligomer represented by the following general formula (1), magnesium oxide nanoparticles and a dispersion medium to obtain a mixed liquid;
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
Removing the dispersion medium from the dispersion,
A method for producing a nanocomposite, comprising:

[In the above formula (1),
R ¹ , R ² , X and Y may be the same or different and each has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Indicates an alkylcarbonyloxy group.
R ^f1 and R ^{f2, which} may be the same or different, each represent (CF ₂ ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F ₇ . (Wherein ^{X 1} represents a hydrogen atom, a fluorine atom, or chlorine atom, n2 the number of 1 to 10, n3 is a number of 0-8.)
n1 shows the number of 1-3, m1 shows the number of 1-10, and m2 shows the number of 0-10. ] The method for producing a nanocomposite according to claim 10, wherein the nanocomposite has a core-shell structure in which a polymer having a fluorine-containing oligomer as a constituent unit is a shell and magnesium oxide nanoparticles are a core. Mixing a fluorine-containing oligomer represented by the following general formula (1), magnesium oxide nanoparticles, and a first dispersion medium to obtain a mixed liquid;
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
Removing the first dispersion medium from the dispersion to obtain a nanocomposite;
Dispersing the nanocomposite in a second dispersion medium,
A method for producing a nanocomposite dispersion, comprising:

[In the above formula (1),
R ¹ , R ² , X and Y may be the same or different and each has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Indicates an alkylcarbonyloxy group.
R ^f1 and R ^{f2, which} may be the same or different, each represent (CF ₂ ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F ₇ . (Wherein ^{X 1} represents a hydrogen atom, a fluorine atom, or chlorine atom, n2 the number of 1 to 10, n3 is a number of 0-8.)
n1 shows the number of 1-3, m1 shows the number of 1-10, and m2 shows the number of 0-10. ] Mixing a fluorine-containing oligomer represented by the following general formula (1), magnesium oxide nanoparticles, and a first dispersion medium to obtain a mixed liquid;
A step of reacting the fluorine-containing oligomer and magnesium oxide nanoparticles with the mixed solution as an alkaline condition to obtain a nanocomposite dispersion;
A method for producing a nanocomposite dispersion, comprising:

[In the above formula (1),
R ¹ , R ² , X and Y may be the same or different and each has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Indicates an alkylcarbonyloxy group.
R ^f1 and R ^{f2, which} may be the same or different, each represent (CF ₂ ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F ₇ . (Wherein ^{X 1} represents a hydrogen atom, a fluorine atom, or chlorine atom, n2 the number of 1 to 10, n3 is a number of 0-8.)
n1 shows the number of 1-3, m1 shows the number of 1-10, and m2 shows the number of 0-10. ] The method for producing a nanocomposite dispersion according to claim 12 or 13, wherein the nanocomposite has a core-shell structure in which a polymer having a fluorine-containing oligomer as a constituent unit is a shell and magnesium oxide nanoparticles are a core. The nanocomposite dispersion according to nanocomposite or claim 6 according to any one of claims 1 to 5 comprising the step of dispersing the organic material, the manufacturing method of the composite material.