JP6875699B2 - Nanocomposite manufacturing method - Google Patents

Description

The present invention relates to a method for producing a nanocomposite and a method for producing a composite material.

With the miniaturization of electronic devices and communication devices, the increase in the amount of signals handled, and the increase in performance such as faster processing speed, heat generation from electronic components is becoming more serious, and the development of resin members with high heat dissipation effect is proceeding. Has been done.

On the other hand, resin members having excellent molding processability and a high degree of freedom in design are also used in automobile-related fields. Due to the miniaturization and performance improvement of automobile products, measures against heat generation, which have not been emphasized until now, have been reviewed, and the demand for high thermal conductivity is increasing.

In recent years, the demand for LED lighting has been increasing due to the growing awareness of the environment. 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 thermal conductive resins are also being actively developed from the viewpoint of weight reduction and the like. .. In addition, it is also important to transmit light in LED lighting and members around the display.

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

In order to solve the above problems, Patent Document 1 forms a layer 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 monovalent alcohol, and the D50 of the magnesium oxide fine particles measured by a dynamic light scattering method is in the range of _{5 to 90 nm.} 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 having excellent water / oil repellency and hydrophilic / oil repellency, Patent Document 3 contains a specific fluorinated terminal chain group and a specific amphipathic group in the main chain skeleton. Nanomaterials and nanocomposites containing fluorine-based compounds are disclosed.

Further, Patent Document 4 discloses a nanocomposite composed of a predetermined fluorine-containing oligomer and / or a polymer thereof and magnesium oxide nanoparticles, and a method for producing the same.

Japanese Unexamined Patent Publication No. 2009-215134 Japanese Unexamined Patent Publication No. 2014-114178 Japanese Unexamined Patent Publication No. 2010-138156 Japanese Unexamined Patent Publication No. 2016-169379

However, in the production method described in Patent Document 1, crystallization is performed by a heating step, 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 production method to nanoparticles.
Further, the magnesium oxide fine particle dispersion of Patent Document 2 is thickened only by being mixed with water on the order of ppm, and is not suitable for use in an aqueous system or in an application where water may be mixed.
As described above, there is still a lack of technology for improving the water resistance of magnesium oxide fine particles whose particle size is controlled to 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 disperses in a liquid dispersion medium or an organic material. Provided is a method capable of efficiently producing a nanocomposite containing magnesium oxide nanoparticles having excellent properties.

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

As described in Patent Document 4, a specific fluorine-containing oligomer having a fluorine group at both ends and an alkoxysilyl group in the main chain skeleton is used, and the nano is obtained by reacting this with magnesium oxide nanoparticles. A composite is formed. In producing this nanocomposite, the present inventors further control the water content in the reaction system, so that the nanocomposite has high water resistance even when the amount of the fluorine-containing oligomer used is relatively small. We have found that composites can be produced efficiently, and have come up with the present invention based on these findings.

The present invention has solved the above-mentioned problems by the following technical configurations.
(I) In a reaction system containing a fluorine-containing oligomer represented by the following general formula (1), magnesium oxide nanoparticles and a dispersion medium, the fluorine-containing oligomer and magnesium oxide nanoparticles are reacted to obtain a nanocomposite. It is a manufacturing method of nanocomposites.
The amount of the fluorine-containing oligomer in the reaction system is 1 to 70 parts by mass with respect to 100 parts by mass of magnesium oxide nanoparticles.
The amount of water in the reaction system is 0.5% by mass or less with respect to the total mass of the fluorine-containing oligomer and magnesium oxide nanoparticles.
Manufacturing method of nanocomposite.

[In the above formula (1),
R ¹ , R ² , X and Y may be the same or different, and the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, or the alkyl group having 1 to 10 carbon atoms, respectively. Indicates an alkylcarbonyloxy group.
R ^f1 and R ^f2 may be the same or different, respectively, and indicate _{(CF 2} ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F _7. (However, X ¹ indicates a hydrogen atom, a fluorine atom, or a chlorine atom, n ₂ indicates a number of 1 to 10, and n ₃ indicates a number of 0 to 8.)
n ₁ represents a number from _{1 to 3, m 1} represents a number from 1 to 10, and m ₂ represents a number from 0 to 10. ]

(II) The method for producing a nanocomposite according to (I) above, wherein the dispersion medium is removed from the reaction system after the reaction between the fluorine-containing oligomer and the magnesium oxide nanoparticles.

(III) The method for producing a nanocomposite according to (II) above, wherein the nanocomposite obtained by removing the dispersion medium is further dispersed in a new dispersion medium.

(IV) The method for producing a nanocomposite according to any one of (I) to (III) above, wherein the fluorine-containing oligomer is a compound represented by the following general formula (1-1).

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

(V) Any of the above (I) to (IV), wherein the nanocomposite is a composite of a polymer having the fluorine-containing oligomer as a constituent unit and magnesium oxide nanoparticles, and has an average particle size of 5 to 500 nm. The method for producing a nanocomposite according to item 1.

(VI) The method for producing a nanocomposite according to any one of (I) to (V) above, wherein the dispersion medium contains one or more organic solvents selected from alcohols, esters, ketones, and ethers.

(VII) The step (A) of obtaining a nanocomposite by the production method according to any one of (I) to (VI) above, and
The step (B) of dispersing the nanocomposite or the nanocomposite dispersion liquid obtained in the step (A) in an organic material, and
A method of manufacturing a composite material, including.

(VIII) The method for producing a composite material according to (VII) above, wherein the organic material is one or more organic materials selected from a resin, a polymerizable monomer and a polymerizable oligomer.

According to the present invention, a nanocomposite that has high water resistance and the like, exhibits high dispersibility in liquids, and can be used as an additive or coating agent that imparts water and oil repellency can be efficiently produced. can do.

(A) is a nanocomposite of Example 1, (b) is a nanocomposite of Example 2, and (c) is a TEM photograph showing magnesium oxide nanoparticles as a raw material.

[Manufacturing method of nanocomposite]
In the present invention, the fluorine-containing oligomer and magnesium oxide nanoparticles are reacted under predetermined conditions in a reaction system containing the fluorine-containing oligomer represented by the general formula (1), magnesium oxide nanoparticles and a dispersion medium. To obtain nanocomposite. In the present invention, the amount of the fluorine-containing oligomer in the reaction system is 1 to 70 parts by mass with respect to 100 parts by mass of magnesium oxide nanoparticles. Further, in the present invention, the amount of water in the reaction system is 0.5% by mass or less with respect to the total mass of the fluorine-containing oligomer and magnesium oxide nanoparticles. Hereinafter, the fluorine-containing oligomer represented by the general formula (1) is referred to as a fluorine-containing oligomer (1).

The fluorine-containing oligomer (1) is a compound represented by the general formula (1).
In the general formula (1), R ¹ and R ² are preferably an alkyl group having 1 to 10 carbon atoms, respectively, and more preferably a methyl group or an ethyl group.
In the 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 the general formula (1), _{the number of m 1} is preferably 1 to 7, and more preferably 2 to 3.
In the general formula (1), m ₂ is preferably a number of 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 , C ₇ F _{15, and the} like. Further, as an example of the perfluorooxaalkyl group of ^{R f1} and R ^f2 _{, -CF (CF 3} ) OC ₃ F ₇ can be mentioned.
^{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 preferably a number of 3 to 7.
In the general formula (1), n ₃ is preferably a number 0 to 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 the general formula (1-1), R ^f3 and R ^f4 are − (CF ₂ ) _p F and −CF (CF ₃ ) O (CF ₂ CFCF ₃ O) _q C ₃ F ₇ (p are, respectively). A number from 1 to 10 and q is a number from 0 to 5). o is a number from 1 to 10. ]

In the general formula (1-1), R ^f3 and R ^f4 are preferably −CF (CF ₃ ) O (CF ₂ CFCF ₃ O) _q C ₃ F ₇ , respectively. Further, p is preferably a number of 3 to 6. Further, q is preferably a number of 0 to 3. The number of o is preferably 2 to 5, and more preferably 2 to 3.

Magnesium oxide nanoparticles are magnesium oxide particles whose particle size is controlled to nano size. The magnesium oxide nanoparticles are not particularly limited, but the average particle size is preferably 5 to 500 nm, more preferably 20 to 100 nm, and even more preferably 20 to 70 nm. This average particle size is measured by a dynamic light scattering method (DLS: Dynamic Light Scattering Measurement). The average particle size can be measured by, for example, a dynamic light scattering photometer. Specifically, the dispersion liquid obtained by stirring and dispersing magnesium oxide nanoparticles with a magnetic stirrer for about 24 hours is used as a dispersion medium. It can be measured using a dynamic light scattering photometer (for example, manufactured by Otsuka Electronics Co., Ltd., model number: DLS-7000HL).

Examples of the dispersion medium include one or more organic solvents selected from alcohols, esters, ketones, and ethers. Examples thereof include alcohols such as methanol, 2-propanol, t-butanol and n-butanol, acetate esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and glycol ethers such as esthetic ethyl cellosolve. In addition to these, 1,1,2,2,3,3,4-heptafluorocyclopentane [Example of commercially available product: Zeorora H (cyclic fluorosolvent manufactured by Nippon Zeon Co., Ltd.)] and 3,3 − Dichloro-1,1,1,2,2-pentafluoropropane / 1,3-dichloro-1,1,2,2,3-pentafluoropropane mixture [Example of commercial product: Asahiclean AK225 (Asahi Glass Co., Ltd.) ), Fluorine-based solvent)] and other fluorine-based solvents can be mentioned.
The dispersion medium preferably contains an alcohol, particularly a dispersion medium selected from monovalent alcohols having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

In the present invention, the amount of water in the reaction system is limited. Therefore, it is preferable not to use water as the dispersion medium.

The dispersion medium is preferably used in a proportion of 5 ml with respect to, for example, 50 to 100 mg of the fluorine-containing oligomer (1). In other words, the amount of the fluorine-containing oligomer (1) per 1 ml of the dispersion medium is preferably 10 to 20 mg.

In the present invention, it is preferable to adjust the amount and type of the dispersion medium so that the fluorine-containing oligomer (1), magnesium oxide nanoparticles and the dispersion medium are mixed to obtain a reaction system as a mixed solution in a sol state. .. The mixture in the sol state preferably has a viscosity of 0.1 mP · s or more, further 0.5 mP · s or more, and 10 mP · s or less, further 5 mP · s or less.

In the present invention, the amount of the fluorine-containing oligomer (1) in the reaction system is 1 to 70 parts by mass with respect to 100 parts by mass of magnesium oxide nanoparticles. The amount of the fluorine-containing oligomer (1) in the reaction system is 1 to 65 parts by mass, further 1 to 60 parts by mass, and further 1 to 60 parts by mass with respect to 100 parts by mass of the magnesium oxide nanoparticles. It is preferably 3 to 50 parts by mass, and more preferably 5 to 40 parts by mass. In the present invention, by using the fluorine-containing oligomer (1) with respect to the magnesium oxide nanoparticles in such an amount, high water resistance is achieved even though the amount of the fluorine-containing oligomer (1) used is relatively small. It is possible to efficiently manufacture nanocomposites equipped with the above. Therefore, when the same water resistance and the like are imparted to the magnesium oxide nanoparticles, the amount of the fluorine-containing oligomer (1) used can be small, which is advantageous in terms of cost. In addition, the production method of the present invention has a high yield, so that a more advantageous effect can be obtained.

In the present invention, the amount of water in the reaction system is determined by the fluorine-containing oligomer (1) from the viewpoint of efficiently obtaining a nanocomposite having excellent water resistance even when the amount of the fluorine-containing oligomer (1) is used. It is 0.5% by mass or less with respect to the total mass of 1) and magnesium oxide nanoparticles. The reaction system may be a mixed solution containing a fluorine-containing oligomer (1), magnesium oxide nanoparticles, a dispersion medium, and other reaction adjusting substances. The amount of water in the reaction system is 0.4% by mass or less, further 0.3% by mass or less, further 0.2% by mass or less, and further based on the total mass of the fluorine-containing oligomer (1) and magnesium oxide nanoparticles. It is preferably 0.1% by mass or less. The reaction system may be substantially water-free, i.e., the water content may be substantially 0% by weight. Here, the fact that the reaction system is substantially free of water or the content of water is substantially 0% by mass is based on the water intentionally added to the reaction system. This means that it is not necessary to target water that is inevitably mixed in the reaction system, such as extremely small amounts of water taken in from the atmosphere and extremely small amounts of water contained in the raw materials used for the reaction.

In the present invention, the amount of water in the reaction system at the start of the reaction may be 0.5% by mass or less with respect to the total mass of the fluorine-containing oligomer (1) and magnesium oxide nanoparticles, and further within the above range. .. The time point at which the reaction starts may be the time when the three components of the fluorine-containing oligomer (1), magnesium oxide nanoparticles, and the dispersion medium first come into contact with each other.
In the reaction targeted by the present invention, the amount of water in the reaction system at the start of the reaction is usually 0.5% by mass or less with respect to the total mass of the fluorine-containing oligomer (1) and magnesium oxide nanoparticles. For example, it is 0.5% by mass or less even at the end of the reaction.

In the method for producing a nanocomposite of the present invention, the amount of water in the dispersion medium used is preferably in the above range. That is, the amount of water in the dispersion medium at the start of the reaction is preferably in the above range.

The method for producing a nanocomposite of the present invention can be carried out without adding water to the reaction system.

In the method for producing a nanocomposite of the present invention, the reaction can be carried out in an open atmosphere such as in the atmosphere, although it depends on conditions such as reaction time. Therefore, the reaction can be carried out under normal pressure. Further, in order to suppress the amount of water taken into the reaction system from the atmosphere, conditions such as performing the reaction in a nitrogen atmosphere or performing the reaction in a closed system may be adopted.

The amount of water in the reaction system can usually be calculated based on the amount of water in each component constituting the reaction system and the amount charged therein.
Further, when the amount of water in the reaction system is considered to be extremely small, it can be measured by the Karl Fischer method. The Karl Fischer method can be performed using, for example, a measuring device manufactured by Hiranuma Sangyo Co., Ltd., model number AQ300.
In the present invention, at least one of the amount of water in the reaction system calculated based on the charged amount and the amount of water in the reaction system measured by the Karl Fischer method may be in the above range.

In the method for producing a nanocomposite of the present invention, a fluorine-containing oligomer (1) is reacted with magnesium oxide nanoparticles in the predetermined reaction system to obtain a nanocomposite. The reaction system may be acidic or alkaline. Alkaline conditions can be obtained by adding a pH adjuster such as ammonia to the reaction system as needed. Acidic conditions can be obtained by adding a pH regulator such as acetic acid to the reaction system as needed.

Although it depends on the type and amount of the reaction raw material, the reaction temperature of the fluorine-containing oligomer (1) and the magnesium oxide nanoparticles can be preferably selected from 0 to 60 ° C, more preferably 10 to 40 ° C.

Although it depends on the type and amount of the reaction raw material, the reaction time between the fluorine-containing oligomer (1) and the magnesium oxide nanoparticles is preferably 10 minutes to 24 hours, more preferably 20 minutes to 10 hours, and further preferably 30 minutes. You can choose from ~ 5 hours.

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

In the present invention, a reaction product is usually obtained as a dispersion liquid containing a nanocomposite and a dispersion medium.

In the method for producing nanocomposites of the present invention, the dispersion medium can be further removed from the reaction mixture after the reaction between the fluorine-containing oligomer (1) and the 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 adopted. 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. Removal of the dispersion medium gives a powder nanocomposite.

The nanocomposite obtained by the production method of the present invention is a complex composed of a fluorine-containing oligomer (1) and magnesium oxide nanoparticles. This complex is a nano-sized complex particle.

The nanocomposite produced according to the present invention is preferably a composite of a polymer having a fluorine-containing oligomer (1) as a constituent unit and magnesium oxide nanoparticles. Further, the nanocomposite produced according to the present invention has a core-shell structure in which a polymer having a fluorine-containing oligomer (1) as a constituent unit is used as a shell and magnesium oxide nanoparticles are used as a core, for example, a fluorine-containing oligomer. A polymer shell having (1) as a constituent unit, in which magnesium oxide nanoparticles as a core are encapsulated, is preferable.

The nanocomposite produced by the present invention is in the form of particles, and the individual particles are not particularly limited in shape, but are preferably spherical or close to spherical. The average particle size of the nanocomposite produced according to the present invention is preferably 5 to 500 nm, more preferably 20 to 100 nm, and even more preferably 20 to 70 nm. This is because if the size is 5 nm or more, the primary particles do not aggregate and the handling becomes easy. On the other hand, when it is 500 nm or less, it is easy to maintain the mechanical properties when blended in a resin film or a resin molded product. Moreover, the transparency of the resin film can be maintained. The average particle size of the nanocomposite produced according to the present invention is measured by a dynamic light scattering method (DLS). The average particle size can be measured by, for example, a dynamic light scattering photometer. Specifically, the nanocomposite is used as a dispersion medium by stirring and dispersing with a magnetic stirrer for about 24 hours, and the obtained dispersion is subjected to dynamic light. It can be measured using a scattered photometer (for example, manufactured by Otsuka Electronics Co., Ltd., model number: DLS-7000HL).

In the method for producing a nanocomposite of the present invention, the nanocomposite obtained by removing the dispersion medium can be further dispersed in a new dispersion medium. As a result, a nanocomposite dispersion liquid obtained by dispersing the nanocomposite in a new dispersion medium can be obtained.
The new dispersion medium can be selected from the dispersion media used in the reaction system.
The new dispersion medium may be of the same type as the dispersion medium used in the reaction system, or may be of a different type.
The new 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. The new dispersion medium preferably has a low water content, for example, 5% by mass or less.
The new dispersion medium is preferably used so that the concentration of the nanocomposite in the obtained nanocomposite dispersion liquid is 5 to 10% by mass, further 10 to 20% by mass, and further 20 to 30% by mass.

The nanocomposite dispersion obtained by the present invention can be applied to a base material and dried to form a film on the surface of the base material. Since this film has a large contact angle with an organic medium such as oleic acid or dodecane and exhibits oil repellency, and also has a large contact angle with water and exhibits antifouling property, the nanocomposite dispersion liquid is water repellent and repellent. It can be used as a coating agent for oils and antifouling agents.

When applying the nanocomposite dispersion obtained by the present invention, for example, the nanocomposite dispersion is sprayed, spun, dip or the like on a base material (metal, glass, rubber, resin, cloth, wood, paper, etc.). It is applied to form a coating film on the surface of the substrate. The coating may be such that the surface of the base material is modified.

As an example of the method for producing a nanocomposite of the present invention,
Step 1 of mixing the fluorine-containing oligomer (1), magnesium oxide nanoparticles, and a dispersion medium to obtain a reaction system, and
Step 2 of reacting the fluorine-containing oligomer (1) with magnesium oxide nanoparticles in the reaction system to obtain a nanocomposite.
A method for manufacturing nanocomposites, including
The amount of the fluorine-containing oligomer (1) and the magnesium oxide nanoparticles in the reaction system is 1 to 70 parts by mass with respect to 100 parts by mass of the magnesium oxide nanoparticles.
The amount of water in the reaction system is 0.5% by mass or less with respect to the total mass of the fluorine-containing oligomer (1) and the magnesium oxide nanoparticles.
A method for producing a nanocomposite can be mentioned.
Further, as another example of the method for producing a nanocomposite of the present invention,
Step 1 of mixing the fluorine-containing oligomer (1), magnesium oxide nanoparticles, and a dispersion medium to obtain a reaction system, and
Step 2 of reacting the fluorine-containing oligomer (1) with magnesium oxide nanoparticles in the reaction system to obtain a nanocomposite.
Step 3 of removing the dispersion medium from the dispersion to obtain a nanocomposite,
A method for manufacturing nanocomposites, including
The amount of the fluorine-containing oligomer (1) and the magnesium oxide nanoparticles in the reaction system is 1 to 70 parts by mass with respect to 100 parts by mass of the magnesium oxide nanoparticles.
The amount of water in the reaction system is 0.5% by mass or less with respect to the total mass of the fluorine-containing oligomer (1) and the magnesium oxide nanoparticles.
A method for producing a nanocomposite can be mentioned.
Further, as another example of the method for producing a nanocomposite of the present invention,
Step 1 of mixing the fluorine-containing oligomer (1), magnesium oxide nanoparticles, and a dispersion medium to obtain a reaction system, and
Step 2 of reacting the fluorine-containing oligomer (1) with magnesium oxide nanoparticles in the reaction system to obtain a nanocomposite.
Step 3 of removing the dispersion medium from the dispersion to obtain a nanocomposite,
Step 4 of dispersing the nanocomposite in a new dispersion medium,
A method for manufacturing nanocomposites, including
The amount of the fluorine-containing oligomer (1) and the magnesium oxide nanoparticles in the reaction system is 1 to 70 parts by mass with respect to 100 parts by mass of the magnesium oxide nanoparticles.
The amount of water in the reaction system is 0.5% by mass or less with respect to the total mass of the fluorine-containing oligomer (1) and the magnesium oxide nanoparticles.
A method for producing a nanocomposite can be mentioned.
Steps 1 to 4 can be carried out according to the corresponding matters of the method for producing a nanocomposite of the present invention described above, and specific examples and preferred embodiments of compounds and the like are also the same.

Further, as another example of the method for producing a nanocomposite of the present invention,
A method for producing a nanocomposite, which comprises reacting a fluorine-containing oligomer (1) with magnesium oxide nanoparticles in a reaction medium to obtain a nanocomposite.
A dispersion medium having a water content of 0.5% by mass or less based on the total mass of the fluorine-containing oligomer (1) and magnesium oxide nanoparticles, and a fluorine-containing oligomer (1), magnesium oxide nanoparticles, and a reaction medium. Mix and
The amount of the fluorine-containing oligomer is 1 to 70 parts by mass with respect to 100 parts by mass of magnesium oxide nanoparticles.
A method for producing a nanocomposite can be mentioned.

[Manufacturing method of composite material]
The present invention
The step (A) of obtaining a nanocomposite by the production method of the present invention and
The step (B) of dispersing the nanocomposite or the nanocomposite dispersion liquid obtained in the step (A) in an organic material, and
To provide a method for producing a composite material, including.

Step (A) is carried out by the method for producing nanocomposites of the present invention.
In step (A), a nanocomposite or nanocomposite dispersion is obtained and used in step (B).

Examples of the organic material used in the step (B) 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 (ureia resin, UF), unsaturated polyester resin (UP), alkyd resin, polyurethane (PUR), and heat curing. Thermo-curable resin such as property polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), polyvinyl acetate (PVAc), polyurethane (PUR), Thermoplastic resin such as ABS resin (acrylonitrile butadiene styrene resin), acrylic resin (PMMA), polyamide (PA) nylon, polyacetal (POM), polycarbonate (PC), modified polyphenylene ether (m-PPE), polyethylene terephthalate (PET) , Engineering plastics such as glass fiber reinforced polyethylene terephthalate (GF-PET), polybutylene terephthalate (PBT), cyclic polyolefin (COP), polyphenylensulfide (PPS), polytetrafluoroethylene (PTFE), polysulfone (PSF), Examples thereof include, but are not limited to, super engineering plastics such as polyether sulfone (PES).

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, trimethylpropantri (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, trimethylol propanetri (meth) acrylate, ditrimethylol propanetetra (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, isobolonyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecandi (meth) Bifunctional monomers such as acrylates, ditrimethylolpropane tetra (meth) acrylates and those modified with PO, EO, etc., pentaerythritol triacrylate (PETA), neopentyl glycol diacrylate (NPGDA), dipentaerythritol hexa. Examples thereof include polyfunctional monomers such as acrylate (DPHA), dipentaerythritol pentaacrylate (DPPA), and trimetyl propanetriacrylate (TMPTA), other functional urethane oligomers, and oligomers such as polyester oligomers. Is not limited.

Further, 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 preferable, but for the purpose of viscosity adjustment or the like, a monofunctional monomer and / or a monofunctional oligomer is used. You can also do it.

In the step (B), the nanocomposite is preferably 0.01 to 1000 parts by mass, more preferably 0.05 to 800 parts by mass, and further preferably 0.1 to 500 parts by mass with respect to 100 parts by mass of the organic material. Use. When the proportion of the nanocomposite used is 0.01 parts by mass or more, the thermal conductivity, water / oil repellency, chemical stability, acid resistance, and surface characteristics of the obtained molded product can be sufficiently improved, and 1000 When it is less than a part by mass, the mechanical properties such as flexibility and elasticity of the obtained resin molded product become good.

For example
Nanocomposite obtained in step (A) on 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-shaped or powder-like resin containing no organic solvent or the like. Alternatively, a nanocomposite dispersion is added, applied to a substrate or the like, and a coating film is formed by thermosetting or photocuring, or after the above-mentioned resin containing no organic solvent is heated and melted and mixed with the nanocomposite. , In the state of being molded into a predetermined shape with a mold,
By doing so, it becomes a composite material.

The fluorine-containing oligomer (1) has a network structure in which the sol-gel reaction proceeds in the state of a composite material. 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 efficiently. As a result, the surface characteristics (stain resistance, water repellency, oil repellency, etc.) of the resin film and the resin molded product are improved.

The surface modified by using the nanocomposite obtained by the present invention exhibits water and oil repellency, and has excellent durability such as heat resistance, chemical resistance, and UV resistance, which are the characteristics of fluorine. Is shown. It is effective for applications that are often exposed to water and ultraviolet rays and are not easy to maintain, and applications where oils and fats, fingerprints, cosmetics, sunscreen creams, human and animal excrement, oil, etc. easily adhere, for example, automobiles and trains. , Window glass or tempered glass for ships, aircraft, skyscrapers, headlamp covers, outdoor equipment, telephone boxes, large outdoor displays, bathtubs, sanitary products such as wash basins, cosmetic tools, kitchen building materials, water tanks, etc. Examples thereof include coatings for preventing fingerprint adhesion of fine arts and the like. In addition, it is also useful as an anti-fingerprint coating for compact discs, DVDs, etc., as a mold release agent or paint additive for molds, and as a resin modifier. In addition, 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, gastrocameras and other medical equipment, copying machines, PCs. , Liquid crystal display, organic EL display, plasma display, touch panel display, protective film, antireflection film and other optical articles. Moreover, since the nanocomposite obtained by the present invention is excellent in water resistance of magnesium oxide and the like, it is suitable as a filler and a filler for a semiconductor encapsulating resin.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the method for producing a nanocomposite according to the present invention is not limited to the following examples. The unit% represents mass% unless otherwise specified.

<Example 1>
At room temperature (25 ° C.), in a sample bottle containing 5 ml of methanol, 167 mg of a fluorine-containing oligomer of the general formula (1-1) and 250 mg of magnesium oxide nanoparticles (average particle size: about 50 nm, Sigma Aldrich Japan Co., Ltd.) were added. In addition, the mixture was stirred for 30 minutes or more. Further, the reaction was carried out at room temperature (25 ° C.) for 5 hours. Here, the completion of the reaction can be confirmed by cloudiness or precipitation of precipitates. The obtained mixture was a dispersion liquid in which nanocomposites of fluorine-containing oligomers / magnesium oxide nanoparticles were dispersed in methanol as a dispersion medium [hereinafter referred to as dispersion liquid (A-1)]. In the fluorine-containing oligomer, R ^f3 and R ^f4 in the general formula (1-1) were -CF (CF ₃ ) OC ₃ F ₇ , respectively, and o was a compound of 2 to 3. As methanol, Wako Pure Chemical Industries, Ltd., a reagent, and a water content of 0.2% by mass or less were used (the same applies to other examples and comparative examples).

After completion of the reaction, methanol was removed from the dispersion (A-1) using an evaporator (80 to 100 ° C.), and then the reaction was stirred again in methanol for several hours to disperse, and then a centrifuge was 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 raw materials used and the yield of nanocomposites.
Further, FIG. 1A shows a TEM (transmission electron microscope) photograph of the nanocomposite obtained in Example 1. In FIG. 1 (a), a part of the grid used for taking the TEM photograph is projected in a blackened state from the center of the image to the lower left. In addition, as FIG. 1 (c), a TEM photograph of magnesium oxide nanoparticles used as a raw material is also shown. From the comparison with FIG. 1 (c), it can be confirmed that the layer covering the magnesium oxide nanoparticles is formed in FIG. 1 (a).

<Examples 2 to 6>
Nanocomposites were obtained in accordance with Example 1 and according to the formulation shown in Table 1 below. The results obtained are shown in Table 1. In Examples 5 and 6, a predetermined amount of water was added to the reaction system immediately before the reaction for 5 hours.
Further, FIG. 1 (b) shows a TEM (transmission electron microscope) photograph of the nanocomposite obtained in Example 2. In FIG. 1 (b), a part of the grid used for taking the TEM photograph is projected in a blackened state from the center of the image to the lower left. From the comparison with FIG. 1 (c), it can be confirmed that the layer covering the magnesium oxide nanoparticles is formed in FIG. 1 (b).

<Comparative example 1>
At room temperature (25 ° C.), in a sample bottle containing 5 ml of methanol, 50 mg of a fluorine-containing oligomer of the general formula (1-1) and 250 mg of magnesium oxide nanoparticles (average particle size: about 50 nm, Sigma Aldrich Japan Co., Ltd.) were added. In addition, the mixture was stirred for 30 minutes or more. Further, 2 ml of water was added, and the mixture was reacted at room temperature (25 ° C.) for 5 hours. Here, the completion of the reaction can be confirmed by cloudiness or precipitation of precipitates. The obtained mixture was a dispersion liquid in which nanocomposites of fluorine-containing oligomers / magnesium oxide nanoparticles were dispersed in methanol as a dispersion medium [hereinafter referred to as dispersion liquid (A-1)]. In the fluorine-containing oligomer, R ^f3 and R ^f4 in the general formula (1-1) were -CF (CF ₃ ) OC ₃ F ₇ , respectively, and o was a compound of 2 to 3.
After completion of the reaction, the same treatment as in Example 1 was carried out to obtain a fluorine-containing oligomer / magnesium oxide nanocomposite as a powder. Table 1 shows the amount of raw materials used and the yield of nanocomposites.

[Water resistance of nanocomposite]
The nanocomposites obtained in Examples 1 to 6 and Comparative Example 1 were collected in an amount of 10 mg in terms of magnesium oxide and placed in a 9 ml sample bottle containing a stirrer (1.5 cm square). 5 ml of water was added thereto. The sample bottle was covered and immersed for 40 hours while stirring at a stirring speed of 1000 rpm. The immersion was performed at an environmental temperature of 25 ° C.
After completion of the immersion, the nanocomposite was collected by centrifugation, washed with methanol, and dried at 70 ° C. for 1 day.
For the dried nanocomposite, the major peak intensities of magnesium oxide and magnesium hydroxide were measured using an XRD diffraction pattern. Using them, the hydrolysis rate (%) was calculated from the following formula, and the water resistance was evaluated. The smaller the hydrolysis rate, the better the water resistance. The results are shown in Table 1.
Hydrolysis rate (%) = X / (X + Y) x 100
X: Peak intensity of the main peak of magnesium hydroxide (peak near 38 °) in the nanocomposite after immersion Y: Peak intensity of the main peak of magnesium oxide (peak near 43 °) in the nanocomposite after immersion

* 1 The number in parentheses for the amount used is the mass part of the fluorine-containing oligomer with respect to 100 parts by mass of magnesium oxide nanoparticles.
* 2 Mass% of water with respect to the total mass of fluorine-containing oligomers and magnesium oxide nanoparticles based on the amount of water added to the reaction system.
* 3 The yield (%) of nanocomposite was derived from the following formula.
Yield of nanocomposite (%) = N / (O + M) x 100
N: Yield of nanocomposite
O: Amount of fluorine-containing oligomer charged
M: Amount of magnesium oxide nanoparticles charged

Claims (8)

A nanocomposite obtained by reacting a fluorine-containing oligomer with magnesium oxide nanoparticles in a reaction system containing a fluorine-containing oligomer represented by the following general formula (1), magnesium oxide nanoparticles, and a dispersion medium. It ’s a manufacturing method,
The amount of the fluorine-containing oligomer in the reaction system is 1 to 20 parts by mass with respect to 100 parts by mass of magnesium oxide nanoparticles.
The amount of water in the reaction system is 0.5% by mass or less with respect to the total mass of the fluorine-containing oligomer and magnesium oxide nanoparticles.
Manufacturing method of nanocomposite.

[In the above formula (1),
R ¹ , R ² , X and Y may be the same or different, and the alkyl group having 1 to 10 carbon atoms, the alkoxy group having 1 to 10 carbon atoms, or the alkyl group having 1 to 10 carbon atoms, respectively. Indicates an alkylcarbonyloxy group.
R ^f1 and R ^f2 may be the same or different, respectively, and indicate _{(CF 2} ) _n2 X ¹ or CF (CF ₃ )-[OCF ₂ CF (CF ₃ )] _n3- OC ₃ F _7. (However, X ¹ indicates a hydrogen atom, a fluorine atom, or a chlorine atom, n ₂ indicates a number of 1 to 10, and n ₃ indicates a number of 0 to 8.)
n ₁ represents a number from _{1 to 3, m 1} represents a number from 1 to 10, and m ₂ represents a number from 0 to 10. ] The method for producing a nanocomposite according to claim 1, wherein the dispersion medium is removed from the reaction system after the reaction between the fluorine-containing oligomer and the magnesium oxide nanoparticles. The method for producing a nanocomposite according to claim 2, wherein the nanocomposite obtained by removing the dispersion medium is dispersed in a new dispersion medium. The method for producing a nanocomposite according to any one of claims 1 to 3, wherein the fluorine-containing oligomer is a compound represented by the following general formula (1-1).

[In the general formula (1-1), R ^f3 and R ^f4 are − (CF ₂ ) _p F and −CF (CF ₃ ) O (CF ₂ CFCF ₃ O) _q C ₃ F ₇ (p are, respectively). A number from 1 to 10 and q is a number from 0 to 5). o is a number from 1 to 10. ] The nano according to any one of claims 1 to 4, wherein the nanocomposite is a composite of a polymer having the fluorine-containing oligomer as a constituent unit and magnesium oxide nanoparticles, and has an average particle size of 5 to 500 nm. How to make a composite. The method for producing a nanocomposite according to any one of claims 1 to 5, wherein the dispersion medium contains one or more organic solvents selected from alcohols, esters, ketones, and ethers. The step (A) of obtaining a nanocomposite by the production method according to any one of claims 1 to 6.
The step (B) of dispersing the nanocomposite or the nanocomposite dispersion liquid obtained in the step (A) in an organic material, and
A method of manufacturing a composite material, including. The method for producing a composite material according to claim 7, wherein the organic material is one or more organic materials selected from a resin, a polymerizable monomer, and a polymerizable oligomer.

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