JP2016169379A - Nanocomposite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a magnesium oxide nanoparticle which has excellent resistance to external effects such as water resistance and acid resistance, effectively exhibits excellent heat conductivity that is inherent to the magnesium oxide nanoparticle, and has an excellent dispersibility into a liquid dispersion medium and an organic material, and to provide a nanocomposite including the magnesium oxide nanoparticle.SOLUTION: There is provided a nanocomposite comprising: a fluorine-containing oligomer represented by formula (1) and/or a polymer thereof; and magnesium oxide nanoparticles. In the formula (1), R, X and Y each independently represent a 1-10C alkyl and alkoxy and the like; Rand Reach independently represent (CF)Xor CF(CF)-[OCFCF(CF)]-OCF; Xrepresents H, F or Cl; nrepresents an integer of 1 to 10; nrepresents an integer of 0 to 8; nrepresents an integer of 1 to 3; mrepresents an integer of 1 to 10; and mrepresents an integer of 0 to 10.SELECTED DRAWING: None

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.

  With the downsizing of electronic equipment and communication equipment, the increase in the amount of signals handled and the increase in processing speed, heat generation from electronic parts has become serious, and the development of resin members with high heat dissipation effects has progressed. It has been.

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

  In recent years, the demand for LED lighting has increased 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 in the past. However, thermal conductive resins are being actively developed from the viewpoint of weight reduction and the like. . In addition, it is also important to transmit light in LED illumination and members around the display.

In order to obtain an efficient heat dissipation effect of the resin, generally, an inorganic powder such as an oxide is added as a filler to increase the thermal conductivity.
Magnesium oxide has the highest thermal conductivity among practical oxide ceramics, has good insulation, is relatively low in hardness, and is inexpensive, so it is expected as a material to be used for heat dissipation fillers. Has been. However, magnesium oxide has a limited range of application as a heat dissipating filler due to poor water resistance.

In order to solve the above problem, in Patent Document 1, a layer is formed on the surface of magnesium oxide to improve water resistance.
Patent Document 2 discloses that 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 the dynamic light scattering method is in the range of ₅ to 90 nm. There is described a magnesium oxide fine particle dispersion having a water content of 9000 mass ppm or less.

  On the other hand, as a material excellent in water / oil repellency effect and hydrophilic / oil repellency effect, Patent Document 3 discloses a specific content having a fluorine-containing terminal chain group and a specific philic group in the main chain skeleton. Nanomaterials and nanocomposites comprising a fluorine compound are disclosed.

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

However, in the manufacturing method described in Patent Document 1, crystallization is performed by a heating process, and the heating temperature at this time is as high as about 1500 ° C. Since it can be easily estimated that nano-sized fine particles are sintered by high-temperature heating and it is difficult to maintain the particle shape and size, it is difficult to adapt this manufacturing method to nanoparticles.
In addition, the magnesium oxide fine particle dispersion of Patent Document 2 thickens only by mixing water in the order of ppm, and is not suitable for use in an aqueous system or in applications where water may be mixed.
Thus, the technique regarding the water resistance improvement of the magnesium oxide fine particle by which the particle size was controlled to nanosize is still insufficient.

  The present invention has good resistance to external influences such as water resistance and acid resistance, can effectively express 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 including magnesium oxide nanoparticles having excellent properties.

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

  As a result of diligent research to solve the above problems, the present inventors used a specific fluorine-containing oligomer having fluorine groups at both ends and having an alkoxysilyl group in the main chain skeleton, and magnesium oxide nanoparticles. It has been found that a nanocomposite is formed by reacting under a alkaline condition. Furthermore, this composite is a nano-sized fine particle. In addition to the extremely high water resistance not seen in conventional magnesium oxide nanoparticles, the surface of the fine particle exhibits high water and oil repellency. Following the amphiphilicity, it has a high affinity for general-purpose organic solvents, and it has been found that these nanoparticles can be easily dispersed in a desired liquid, and that the surface of the substrate can be modified with this dispersion. The present invention was made based on these findings.

The present invention has solved the above problems by the following technical configuration.
(I) 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. An alkylcarbonyloxy group is shown.
R ^f1 and R ^f2 may be the same or different and each represents (CF ₂ ) _{n 2} X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _{n 3} —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 represents a number of ₁ to 3, m ₁ represents a number of ₁ to 10, and m ₂ represents a number of 0 to 10. ]

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

[In General Formula (1-1), R ^f3 and R ^f4 are respectively-(CF ₂ ) _p F and -CF (CF ₃ ) O (CF ₂ CFCF ₃ O) _q C ₃ F ₇ (p is 1 to 10 and q is a number from 0 to 5). o is a number from 1 to 10. ]

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

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

(V) A nanocomposite dispersion obtained by dispersing the nanocomposite according to any 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 a resin, a polymerizable monomer, and a polymerizable oligomer
The composite material according to the above (VI), which is an organic material of at least species.

(VIII) The coating agent comprised including the nanocomposite dispersion liquid as described in said (V).

(IX) a step of mixing the fluorine-containing oligomer represented by the general formula (1), the magnesium oxide nanoparticles and the dispersion medium to obtain a mixed solution;
A step of reacting a fluorine-containing oligomer and magnesium oxide nanoparticles under alkaline conditions of the mixed liquid 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 a fluorine-containing oligomer and magnesium oxide nanoparticles under alkaline conditions of the mixed liquid 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.

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

(XII) The nanocomposite according to any one of (I) to (IV) or (V)
The manufacturing method of a composite material including the process of disperse | distributing the nanocomposite dispersion liquid of description to organic material.

  The nanocomposite of the present invention not only imparts high water resistance and the like to the magnesium oxide nanoparticles, but the nanocomposite or its dispersion exhibits high dispersibility with respect to the liquid due to the effect due to fluorine, and the water repellent properties. -It can be used as an additive or coating agent that imparts oil repellency.

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

  Hereinafter, the nanocomposite of the present invention, the dispersion thereof, the composite material containing the nanocomposite, the coating agent containing the dispersion, and the production methods thereof will be described.

[Nanocomposite]
The nanocomposite of the present invention is a composite comprising 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. An alkylcarbonyloxy group is shown.
R ^f1 and R ^f2 may be the same or different and each represents (CF ₂ ) _{n 2} X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _{n 3} —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 represents a number of ₁ to 3, m ₁ represents a number of ₁ to 10, and m ₂ represents a number of 0 to 10. ]

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), X and Y are each preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably a methoxy group or an ethoxy group.
In the general formula (1), m ₁ is preferably a number from 1 to 7, and more preferably from 2 to 3.
In the general formula (1), _{m 2} is preferably a number of 0 to 5, more preferably 0.
In the general formula ^{(1), R f1} and ^{R f2 _{are, (CF 2) n2 X 1}} , or _{CF (CF} 3) - perfluoro represented by _{[OCF 2 CF (CF 3)} ] n3 -OC 3 F 7 Examples of the alkyl group 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 from 1 to 3.
In the general formula (1), _{n 2} is the number of 3-7 is preferable.
In the general formula (1), _{n 3} is preferably several of 0-3.
The number may be an integer.

  As the fluorine-containing oligomer (1), a compound represented by the following general formula (1-1) is preferable.

[In General Formula (1-1), R ^f3 and R ^f4 are respectively-(CF ₂ ) _p F and -CF (CF ₃ ) O (CF ₂ CFCF ₃ O) _q C ₃ F ₇ (p is 1 to 10 and q is a number from 0 to 5). o is a number from 1 to 10. ]

In general formula (1-1), R ^f3 and R ^f4 are each preferably —CF (CF ₃ ) O (CF ₂ CFCF ₃ O) _q C ₃ F ₇ . Moreover, p is preferably a number from 3 to 6. Moreover, q is preferably a number from 0 to 3. o is preferably 2 to 5, more preferably 2 to 3.

  Magnesium oxide nanoparticles are magnesium oxide particles whose particle size is controlled to nanosize. 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 average particle diameter of the magnesium oxide nanoparticles is 5 to 500 nm, and more preferably 10 to 50 nm. It is preferable that This average particle diameter is measured by a dynamic light scattering method (DLS: Dynamic Light Scattering Measurement). The average particle diameter can be measured by, for example, a dynamic light scattering photometer. Specifically, magnesium oxide nanoparticles are stirred and dispersed in a dispersion medium with a magnetic stirrer for about 24 hours. It can be measured using a dynamic light scattering photometer (for example, model number: DLS-7000HL, manufactured by Otsuka Electronics Co., Ltd.).

  The nanocomposite of the present invention is preferably a composite of a polymer having a fluorine-containing oligomer (1) as a structural unit and magnesium oxide nanoparticles. Furthermore, the nanocomposite of the present invention has a core-shell structure in which a polymer containing the fluorine-containing oligomer (1) as a structural unit is used as a shell and magnesium oxide nanoparticles are used as a core, such as a fluorine-containing oligomer (1). A shell made of a polymer having a structural unit of and encapsulating magnesium oxide nanoparticles as a core is preferable.

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

The present invention includes a nanocomposite obtained by reacting the fluorine-containing oligomer (1) with magnesium oxide nanoparticles.
The present invention includes a nanocomposite obtained by reacting the fluorine-containing oligomer (1) in the presence of magnesium oxide nanoparticles.
The present invention includes a nanocomposite in which a polymer of fluorine-containing 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, and still more preferably 20 to 70 nm. If the thickness is less than 5 nm, the primary particles aggregate and the handling becomes difficult. On the other hand, when the thickness exceeds 500 nm, mechanical properties may be deteriorated when blended into a resin film or a resin molded product. There is also a concern that the transparency of the resin film may be impaired. The average particle size of the nanocomposite of the present invention is measured by a dynamic light scattering method (DLS: Dynamic Light Scattering Measurement). The average particle diameter can be measured by, for example, a dynamic light scattering photometer. Specifically, the nanocomposite is stirred and dispersed with a magnetic stirrer for about 24 hours in a dispersion medium, and the resulting dispersion is subjected to dynamic light. 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 fluorine-containing 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. 100 parts by mass is more preferable.

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

As a method for producing the nanocomposite of the present invention,
Mixing the fluorine-containing oligomer represented by the general formula (1), the magnesium oxide nanoparticles, and the dispersion medium to obtain a mixed solution;
A step of reacting a fluorine-containing oligomer and magnesium oxide nanoparticles under alkaline conditions of the mixed liquid 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 manufacturing method 1, 5-400 mass parts is preferable, as for the ratio of the fluorine-containing oligomer (1) with respect to 100 mass parts of magnesium oxide nanoparticles, 10-200 mass parts is more preferable, and 20-100 mass parts is still more preferable. If the ratio exceeds 400 parts by mass, the production cost may increase due to material costs, 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 sufficient surface properties (antifouling, water repellency, oil repellency, etc.) may not be obtained for organic materials.

Examples of the dispersion medium include acetates such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, glycol ethers such as este 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: Zeolora H (cyclic fluorinated 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: Asahiklin AK225 (manufactured by Asahi Glass Co., Ltd., fluorinated solvent) , Etc., but not limited thereto.
The dispersion medium preferably contains a dispersion medium selected from alcohols, especially monohydric alcohols having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, and 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 the production method 1, it is preferable to adjust the amount and type of the fluorinated oligomer (1), the magnesium oxide nanoparticles, and the dispersion medium so that a mixed solution in a sol state can be obtained.

  Production method 1 has a step of obtaining a nanocomposite dispersion by reacting the fluorine-containing oligomer and magnesium oxide nanoparticles using the mixed solution obtained in the above step, preferably a sol-state mixed solution, under alkaline conditions. The alkaline condition can be 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. As for the alkaline condition, the pH is preferably 8 to 14, and 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.

  Although depending on the kind and amount of the reaction raw material, the reaction temperature between 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 type 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, and even more preferably 30 minutes to 5 hours. You can choose from.

  The completion of the reaction between the fluorine-containing oligomer and the magnesium oxide nanoparticles can be confirmed by the occurrence of white turbidity or precipitation of precipitates. Upon completion of the reaction, a nanocomposite dispersion containing the fluorine-containing oligomer (1) and / or polymer thereof and magnesium oxide nanoparticles is obtained.

  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 a polymer thereof and magnesium oxide nanoparticles. For the removal of the dispersion medium, a known method according to the type and amount of the dispersion medium can be employed. 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 powder 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 nanocomposite and the use of the dispersion.
The dispersion medium of the nanocomposite dispersion liquid can be selected from the dispersion media listed in Production Method 1.

  The nanocomposite dispersion of the present invention can be applied to a substrate and dried to form a coating on the substrate surface. Since this coating has a large contact angle with organic media such as oleic acid and dodecane, and exhibits oil repellency, and also has a large contact angle with water and antifouling properties, the nanocomposite dispersion has water and water repellency. It can be used as a coating agent such as an oil agent or an antifouling agent. Therefore, this invention provides the coating agent comprised including the nanocomposite dispersion liquid of this invention.

  When applying the nanocomposite dispersion of the present invention, for example, the nanocomposite dispersion is applied to a substrate (metal, glass, rubber, resin, fabric, wood, paper, etc.) by spraying, spinning, dip, etc. A coating film is formed on the substrate surface. Application | coating may be the grade which modifies the surface of a base material.

  Although the manufacturing method of the nanocomposite dispersion liquid of this invention is shown below, it is not limited to this.

The nanocomposite dispersion of the present invention can be prepared by redispersing the nanocomposite obtained by the production method 1 in a dispersion medium.
In addition, the nanocomposite dispersion of the present invention can be prepared by adopting the steps up to the last 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 fluorine-containing oligomer (1).

Specific examples of the method for producing the nanocomposite dispersion of the present invention include the following.
Mixing the fluorine-containing oligomer represented by the general formula (1), the magnesium oxide nanoparticles, and the first dispersion medium to obtain a mixed solution;
A step of reacting a fluorine-containing oligomer and magnesium oxide nanoparticles under alkaline conditions of the mixed liquid 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 (hereinafter referred to as production method 2).

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

In production methods 2 and 3, steps common to production method 1 can be performed in the same manner as in production method 1. The first dispersion medium of production method 2 corresponds to the dispersion medium of production method 1.
In the production method 2, in the step of dispersing the nanocomposite in the second dispersion medium, the second dispersion medium may be the same type as the first dispersion medium or a different type. Each of the first and second dispersion media can be selected from the dispersion media mentioned in Production Method 1. In production method 2, the second dispersion medium is preferably an alcohol, a monohydric alcohol having 1 to 6 carbon atoms, and further 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 nanocomposite of the present invention or the 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 a sol-gel reaction proceeds. This fluorine-containing oligomer (1) is high on the surface of the finally obtained resin film or resin molded product because fluorine atoms (atoms that contribute to the improvement of surface characteristics) are selectively introduced at both ends. Fluorine atoms can be present with efficiency. Thereby, 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 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), thermosetting Thermosetting resin such as conductive polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polyurethane (PUR), Thermoplastic resins such as ABS resin (acrylonitrile butadiene styrene resin) and acrylic resin (PMMA), polyamide (PA) nylon, polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE), polyethylene terephthalate (PET) , Glass phi -Engineering plastics such as reinforced polyethylene terephthalate (GF-PET), polybutylene terephthalate (PBT), cyclic polyolefin (COP), polyphenylene sulfide (PPS), polytetrafluoroethylene (PTFE), polysulfone (PSF), polyether Although super engineering plastics, such as a sulfone (PES), can be mentioned, It is not limited to these.

  The polymerizable monomer and / or oligomer is preferably a polyfunctional monomer and / or oligomer having two or more polymerizable functional groups (that is, bifunctional). 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 ) 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. Bifunctional 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 bifunctional or higher monomers and / or bifunctional or higher oligomers are suitable, but monofunctional monomers and / or monofunctional oligomers are used for the purpose of viscosity adjustment and the like. 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. Part by mass. If the amount is less than 0.01 parts by mass, the heat conductivity, water / oil repellency, chemical stability, acid resistance, and surface characteristics of the obtained molded product cannot be sufficiently improved. This is because the resulting resin molded product may cause deterioration in mechanical properties such as flexibility and elasticity.

Although the manufacturing method of the composite material of this invention is shown below, it is not limited to this.
Examples of the method for producing a composite material of the present invention include a method for producing a composite material including a step of dispersing the nanocomposite of the present invention or the nanocomposite dispersion of the present invention in an organic material.

  For example, the nanocomposite or nanocomposite of the present invention may be applied to 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 powdery resin not containing an organic solvent. Add the dispersion, apply to the substrate, etc., form a coating film by thermosetting or photocuring, or the resin that does not contain the organic solvent is heated and melted and mixed with the nanocomposite, then the mold Thus, a composite material can be obtained by forming into a predetermined shape.

  The surface modified by using the nanocomposite of the present invention exhibits water repellency and oil repellency, and exhibits excellent properties 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 for oils and fingerprints, cosmetics, sunscreen, human and animal excrement, oil, etc. Window glass or tempered glass for ships, aircraft, high-rise buildings, headlamp covers, outdoor equipment, telephone boxes, outdoor large displays, sanitary products such as bathtubs, washbasins, makeup tools, kitchen building materials, water tanks, Examples include anti-fingerprint coatings for artworks. In addition, it is also useful as a fingerprint preventive coating for compact discs, DVDs, etc., as a mold release agent or paint additive for resin molds, and as a resin modifier. In addition, medical devices such as car navigation systems, mobile phones, digital cameras, digital video cameras, PDAs, portable audio players, car audio systems, game machines, eyeglass lenses, camera lenses, lens filters, sunglasses, gastric cameras, copying machines, PCs Development to optical articles such as liquid crystal displays, organic EL displays, plasma displays, touch panel displays, protective films, and antireflection films can be considered. Moreover, since the nanocomposite of this invention is excellent in the water resistance etc. of magnesium oxide, it is suitable as a filler and also as a filler for semiconductor sealing resin.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the nanocomposite, the nanocomposite dispersion and the production method thereof according to the present invention are not limited to the following examples. Note that the unit% represents mass% unless otherwise specified.

<Example 1>
At room temperature (25 ° C.), in a sample bottle to which 5 ml of methanol was added, 200 mg of the fluorine-containing oligomer of general formula (1-1) and 50 mg of magnesium oxide nanoparticles (average particle size: about 50 nm, Sigma-Aldrich Japan Co., Ltd.) In addition, the mixture was stirred for 30 minutes or more. Further, at room temperature (25 ° C.), 2 ml of 25% aqueous ammonia was added and reacted for 5 hours. Here, the completion of the reaction can be confirmed by cloudiness or sedimentation of precipitates. The resulting mixture was a dispersion (hereinafter referred to as dispersion (A-1)) in which a nanocomposite of fluorine-containing oligomer / magnesium oxide nanoparticles was dispersed in methanol as a dispersion medium. Incidentally, the fluorine-containing oligomer, ^{R f3} and ^{R f4} in the general formula (1-1), respectively, a _{-CF (CF 3) OC 3 F} 7, o is a compound 2-3.

  After completion of the reaction, methanol is removed from the dispersion (A-1) using an evaporator (80 to 100 ° C.), and then the reaction product is stirred and dispersed again in methanol for several hours. Further, using a centrifuge, 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, and then a fluorine-containing oligomer / magnesium oxide nanocomposite was obtained as a powder. Table 1 shows the amount of raw material used, the yield of the nanocomposite, and the average particle size of the nanocomposite.

<Examples 2 to 4>
In accordance with Example 1, nanocomposites were obtained in accordance with the formulation shown in Table 1 below. The obtained results are shown in Table 1. In addition, the dispersion liquid of the nanocomposite obtained in the manufacturing process of Examples 2-4 was made into the dispersion liquid (A-2), the dispersion liquid (A-3), and the dispersion liquid (A-4), respectively.

* 1 The number in parentheses for the amount used is the part by mass of the fluorine-containing oligomer with respect to 100 parts by mass of the magnesium oxide nanoparticles (the same applies to Table 2).
* 2 The nanocomposite yield (%) was derived from the following equation.
Nanocomposite yield (%) = X / (Y + Z) × 100
X: Yield of nanocomposite
Y: Preparation amount of fluorine-containing oligomer
Z: Preparation amount of magnesium oxide nanoparticles * 3 The average particle size was measured by a dynamic light scattering method (DLS: Dynamic Light Scattering Measurement) (manufactured by Otsuka Electronics Co., Ltd., model number: DLS-7000HL).

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

[Dispersibility of nanocomposites]
The dispersibility of the nanocomposite obtained in Example 4 was evaluated as follows.
A dispersion prepared by dispersing magnesium oxide nanoparticles (untreated / same as in Example 1) in methanol, and a dispersion prepared by dispersing the fluorine-containing oligomer / magnesium oxide nanocomposite of Example 4 in methanol. About 2 types, the state of particle | grains was observed and evaluated with FE-SEM (Field emission type | mold (Field Emission (Scanning electron microscope)) (JEOL Co., Ltd. make, model number: JSM-7000F). The results are shown in FIG.

FIG. 1A is an FE-SEM photograph of a dispersion of untreated magnesium oxide nanoparticles as a comparative example.
1B is an FE-SEM photograph of the fluorine-containing oligomer / magnesium oxide nanocomposite of Example 4. FIG.
As shown in FIG. 1A (comparative example), magnesium oxide nanoparticles alone cannot be dispersed up to primary particles. In contrast, the nanocomposite of Example 4 could be monodispersed in methanol (see FIG. 1B).
As described above, the fluorine-containing oligomer having fluorine atoms introduced at both ends forms a molecular assembly and serves as a so-called dispersant. After the magnesium oxide nanoparticles are dispersed to the primary particles, It shows that the fluorine-containing oligomer and the magnesium oxide nanoparticles are combined.

[Water resistance of nanocomposites]
The water resistance of the nanocomposites obtained in Examples 1 and 4 was evaluated as follows.
The nanocomposites of Examples 1 and 4 in an amount corresponding to 10 mg of untreated magnesium oxide nanoparticles and a magnesium oxide content of 10 mg calculated from a thermogravimetric analyzer (TGA) were each immersed in water (5 ml) and magnetic. The mixture was stirred and dispersed with a stirrer for a predetermined time. Thereafter, 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 in increments of 20 hours from the start of immersion to 120 hours later, and powder was obtained at each time, and the XRD pattern was measured. The results are shown in FIG. In addition, Bruker AXS Co., Ltd. make and model number: TG-DTA2000SA was used for the thermogravimetric analyzer.

FIG. 2A is an XRD pattern of untreated magnesium oxide nanoparticles as a comparative example.
FIG. 2 (B) 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), untreated magnesium oxide nanoparticles produced a magnesium hydroxide pattern by immersion in water for 20 hours, whereas FIG. 2 (B). As shown in FIG. 2C, the nanocomposites of Examples 1 and 4 have no magnesium hydroxide pattern even when immersed in water for 120 hours, and can maintain the crystal structure of magnesium oxide. I understand that.

[Nanocomposite acid resistance]
The acid resistance of the nanocomposites obtained in Examples 1 and 4 was evaluated as follows.
The nanocomposites of Examples 1 and 4 in an amount corresponding to 10 mg of untreated magnesium oxide nanoparticles and a magnesium oxide content of 10 mg calculated from a thermogravimetric analyzer (TGA) were each in a 0.5 mM hydrochloric acid solution (1 ml). For 48 hours. Thereafter, 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: MiniFlex600). However, since the untreated magnesium oxide was completely dissolved in the solution, the solvent was removed at 100 ° C. and dried for 1 day to precipitate powder. The results are shown in FIG. In addition, Bruker AXS Co., Ltd. make and model number: TG-DTA2000SA was used for the thermogravimetric analyzer.

  From the results of the XRD shown in FIG. 3, the untreated magnesium oxide nanoparticles have a magnesium chloride pattern formed by immersion in hydrochloric acid for 48 hours, whereas the nanocomposites of Examples 1 and 4 are chlorinated. It can be seen that the magnesium pattern is not generated and the crystal structure of magnesium oxide can be maintained.

[Thermal decomposition behavior of nanocomposites]
About the thermal decomposition behavior of the fluorine-containing oligomer / magnesium oxide nanocomposite obtained in Examples 1 to 4, using a thermogravimetric analyzer (TGA), the temperature was increased from room temperature to 800 ° C. at a temperature rising rate of 10 ° C./min. Until measured. As the thermogravimetric analyzer, Bruker AXS Co., Ltd., model number: TG-DTA2000SA was used. The obtained results are shown in FIG. In FIG. 3, the comparative example is the result for untreated magnesium oxide nanoparticles.

  From the TGA results shown in FIG. 3, it can be confirmed that the degree of mass decrease 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. The results are shown in FIG.
As shown in FIG. 4, a peak considered to be derived from MgF ₂ that was not observed before the heat treatment was observed together with the MgO peak. These results show that this nanocomposite does not release harmful HF generated when the fluorine compound is thermally decomposed, that is, magnesium oxide can trap fluorine by forming a stable Mg-F bond. Yes.

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

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 water and dodecane on the modified surface thus obtained was measured. The contact angle was measured with a contact angle measuring device (manufactured by 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, the dispersion (A-3) prepared in Example 3 in Example 7, and the dispersion prepared in Example 4 in Example 8. Using (A-4), a modified glass slide was obtained in accordance with Example 5. 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 repellency and super oil repellency. In particular, in Examples 5 and 6 in which the content of the fluorine-containing oligomer was high, the oil contact angle showed a super oil repellency of 100 ° or more. This is considered to be because, in addition to the surface unevenness effect formed by the nanocomposite, the so-called Lotus effect, the unreacted fluorine-containing oligomer lowers the surface energy and further improves the oil repellency.

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

The nanocomposite content in the modified PMMA films of Examples 9-12 is 1%.
As shown in Table 3, the film modified by the nanocomposite of the present invention exhibited higher water repellency and oil repellency on the surface than on the film back surface. Normal plastics are oleophilic. That is, it can be seen that the back surface has the same performance as the conventional plastic (dodecane: 0 °), but the oil repellent attributed 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 the PMMA film modified by the above method is produced, the solvent is removed from the solution in which the nanocomposite is dispersed in the petri dish. Thus, it can be estimated that the nanocomposite moves to the vicinity of the film surface.

Claims (12)

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. An alkylcarbonyloxy group is shown.
R ^f1 and R ^f2 may be the same or different and each represents (CF ₂ ) _{n 2} X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _{n 3} —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 represents a number of ₁ to 3, m ₁ represents a number of ₁ to 10, and m ₂ represents a number of 0 to 10. ] The nanocomposite according to claim 1, wherein the fluorine-containing oligomer is a compound represented by the following general formula (1-1).

[In General Formula (1-1), R ^f3 and R ^f4 are respectively-(CF ₂ ) _p F and -CF (CF ₃ ) O (CF ₂ CFCF ₃ O) _q C ₃ F ₇ (p is 1 to 10 and q is a number from 0 to 5). o is a number from 1 to 10. ]   The nanocomposite according to claim 1 or 2, wherein a polymer containing the fluorine-containing oligomer as a constituent unit and magnesium oxide nanoparticles are combined, and the average particle size is 5 to 500 nm.   The nanocomposite according to any one of claims 1 to 3, wherein a ratio of the fluorine-containing oligomer and / or a polymer thereof to 100 parts by mass of the magnesium oxide nanoparticles is 5 to 400 parts by mass.   A nanocomposite dispersion obtained by dispersing the nanocomposite according to any one of claims 1 to 4 in a dispersion medium.   The composite material formed by disperse | distributing the nanocomposite of any one of Claims 1-4, or the nanocomposite dispersion liquid of Claim 5 to the organic material.   The composite material according to claim 6, wherein the organic material is one or more organic materials selected from resins, polymerizable monomers, and polymerizable oligomers.   A coating agent comprising the nanocomposite dispersion according to claim 5. 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 solution;
A step of reacting a fluorine-containing oligomer and magnesium oxide nanoparticles under alkaline conditions of the mixed liquid 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. An alkylcarbonyloxy group is shown.
R ^f1 and R ^f2 may be the same or different and each represents (CF ₂ ) _{n 2} X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _{n 3} —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 represents a number of ₁ to 3, m ₁ represents a number of ₁ to 10, and m ₂ represents a number of 0 to 10. ] A step of mixing a fluorine-containing oligomer represented by the following general formula (1), magnesium oxide nanoparticles and a first dispersion medium to obtain a mixed solution;
A step of reacting a fluorine-containing oligomer and magnesium oxide nanoparticles under alkaline conditions of the mixed liquid 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.

[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. An alkylcarbonyloxy group is shown.
R ^f1 and R ^f2 may be the same or different and each represents (CF ₂ ) _{n 2} X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _{n 3} —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 represents a number of ₁ to 3, m ₁ represents a number of ₁ to 10, and m ₂ represents a number of 0 to 10. ] A step of mixing a fluorine-containing oligomer represented by the following general formula (1), magnesium oxide nanoparticles and a first dispersion medium to obtain a mixed solution;
A step of reacting a fluorine-containing oligomer and magnesium oxide nanoparticles under alkaline conditions of the mixed liquid to obtain a nanocomposite dispersion;
A method for producing a nanocomposite dispersion.

[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. An alkylcarbonyloxy group is shown.
R ^f1 and R ^f2 may be the same or different and each represents (CF ₂ ) _{n 2} X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _{n 3} —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 represents a number of ₁ to 3, m ₁ represents a number of ₁ to 10, and m ₂ represents a number of 0 to 10. ]   The manufacturing method of a composite material including the process of disperse | distributing the nanocomposite of any one of Claims 1-4, or the nanocomposite dispersion liquid of Claim 5 to an organic material.