JP2010235441A - Magnetic iron oxide nanocomposite powdery particle, method of manufacturing the same, particle dispersion liquid, and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magnetic iron oxide nanocomposite powdery particle which is highly dispersed for various solvents at a level of several tens of nanometers and has persistency in dispersibility. <P>SOLUTION: The magnetic iron oxide nanocomposite powdery particle is characterized in that magnetic iron oxide particles are combined with fluoroalkyl group-containing oligomer represented by the general formula (1). In the formula, R<SP>1</SP>and R<SP>2</SP>represent -(CF<SB>2</SB>)p-Y group or -CF(CF<SB>3</SB>)-[OCF<SB>2</SB>CF(CF<SB>3</SB>)]q-OC<SB>3</SB>F<SB>7</SB>group, R<SP>1</SP>and R<SP>2</SP>may be the same or different from each other, Y in R<SP>1</SP>and R<SP>2</SP>represents hydrogen atom, fluorine atom or chlorine atom, and p and q denote integers of 0 to 10. B<SB>1</SB>represents 1-5C alkylene group, n3 denotes an integer of 5 to 1,000, and molar ratio of n1 to n2 is in the range of 1/99 to 99/1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to magnetic iron oxide nanocomposite powder particles having magnetism, a production method thereof, a particle dispersion containing the composite powder particles, and a resin composition.

  Ferromagnetic iron oxides such as magnetite are chemically stable and relatively large magnetized fine particles, and thus have been widely used in various applications such as magnetic recording media, magnetic fluids, and magnetic toners.

  In recent years, the application of magnetic iron oxide particles to medical and biotechnology fields such as magnetic concentration / separation carriers in immunoassay has been expanding, and it has been regarded as very important in conventional applications. Various properties that were not available have been required for iron oxide particles. For example, characteristics such as better particle shape or particle size compared to the prior art and good dispersion in a solvent have been demanded.

  The present inventors previously have an oligomer skeleton containing at least a unit having a hydrophilic group as magnetic iron oxide that can be dispersed at a nano to micron level in water, an organic solvent, and a polymer material, A dispersible magnetic iron oxide containing a modifying group composed of a fluorine-containing oligomer having a skeleton end composed of a polyfluoroalkyl group was proposed (see Patent Document 1).

JP 2005-289794 A

  The present inventors further conducted research on magnetic iron oxide that is highly dispersed at several tens of nanometers in various solvents and has a long dispersibility. It has been found that when iron oxide is combined, dispersibility and dispersion sustainability are further improved, and the present invention has been completed.

  That is, the object of the present invention is to provide magnetic iron oxide nanocomposite powder particles that are highly dispersed at several tens of nanometers in various solvents and have a sustained dispersibility, an industrially advantageous production method thereof, The object is to provide a particle dispersion and a resin composition in which magnetic iron oxide nanocomposite powder particles are highly dispersed.

A first invention provided by the present invention is a magnetic iron oxide nanocomposite powder in which magnetic iron oxide particles are complexed with a fluoroalkyl group-containing oligomer represented by the following general formula (1): Particles.

{In the formula, R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. is there. B ₁ represents an alkylene group having 1 to 5 carbon atoms. n3 is an integer of 5 to 1000. The molar ratio of n1 and n2 is 1:99 to 99: 1. }

The second invention provided by the present invention is characterized in that the magnetic iron oxide particles are complexed with a crosslinking reaction product of a fluoroalkyl group-containing oligomer represented by the following general formula (2). Magnetic iron oxide nanocomposite powder particles.

{Wherein R ³ and R ⁴ represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ³ And R ⁴ may be the same group or different groups, Y in R ³ and R ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. is there. Z represents an isocyanate-containing group. m3 is an integer of 5 to 1000. The molar ratio of m1 and m2 is 1:99 to 99: 1. }

  According to a third aspect of the present invention, there is provided a magnetic iron oxide nanoparticle characterized by contacting magnetic iron oxide particles with a fluoroalkyl group-containing oligomer represented by the general formula (1) in a solvent. This is a method for producing composite powder particles.

  The fourth invention provided by the present invention is a method for producing magnetic iron oxide by adding an alkali to a solvent containing a ferrous salt and a ferric salt, and producing the magnetic iron oxide. It is a method for producing magnetic iron oxide nanocomposite powder particles characterized by containing a fluoroalkyl group-containing oligomer represented by formula (1) and adding an alkali to react.

  The fifth invention provided by the present invention is to prepare a solvent containing magnetic iron oxide particles and a fluoroalkyl group-containing oligomer represented by the general formula (2), and then represented by the general formula (2). It is a method for producing magnetic iron oxide nanocomposite powder particles characterized in that a cross-linking reaction of a fluoroalkyl group-containing oligomer is performed.

  The sixth invention provided by the present invention is a particle dispersion characterized in that the magnetic iron oxide nanocomposite powder particles of the first and second inventions are dispersed in a dispersion solvent. .

  The seventh invention provided by the present invention is a resin composition comprising the magnetic iron oxide nanocomposite powder particles of the first and second inventions.

  According to the present invention, it is possible to provide magnetic iron oxide nanocomposite powder-like particles having extremely high dispersibility of several tens of nanometers in various solvents and having a long dispersibility. In addition, according to the present invention, the magnetic iron oxide nanocomposite powder particles can be provided by an industrially advantageous method.

The FT-IR chart of the magnetic iron oxide nanocomposite powder-like particle | grains obtained in Examples 1-6. The X-ray-diffraction figure of the magnetic iron oxide nanocomposite powder-like particle | grains obtained in Examples 1-4. The X-ray-diffraction figure of the magnetic iron oxide nanocomposite powder-like particle | grains obtained in Examples 5-6. 4 is a TEM photograph of magnetic iron oxide nanocomposite powder particles obtained in Example 2. FIG. The figure which shows the time-dependent change of the light transmittance in the light absorbency 500nm of the dispersion liquid which disperse | distributed the magnetic iron oxide nanocomposite powder-form particle obtained in Examples 1-3 to methanol. The figure which shows the time-dependent change of the relative turbidity in the light absorbency 500nm of the dispersion liquid which disperse | distributed the magnetic iron oxide nanocomposite powder-form particle obtained in Examples 1-3 to methanol. The FT-IR chart of the magnetic iron oxide nanocomposite powder-like particle | grains obtained in Examples 12-14. The X-ray-diffraction figure of the magnetic iron oxide nanocomposite powder-like particle | grains obtained in Examples 12-14. 4 is a TEM photograph of magnetic iron oxide nanocomposite powder particles obtained in Example 14. FIG. 4 is a TEM photograph of magnetic iron oxide nanocomposite powder particles obtained in Example 22. FIG.

Hereinafter, the present invention will be described based on preferred embodiments thereof.
The magnetic iron oxide nanocomposite powdery particles of the first invention according to the present invention are characterized in that the magnetic iron oxide particles are complexed with a fluoroalkyl group-containing oligomer represented by the following general formula (1). To do.

{In the formula, R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. is there. B ₁ represents an alkylene group having 1 to 5 carbon atoms. n3 is an integer of 5 to 1000. The molar ratio of n1 and n2 is 1:99 to 99: 1. }

In addition, in the magnetic iron oxide nanocomposite powder particles of the second invention according to the present invention, the magnetic iron oxide particles are combined with a crosslinking reaction product of a fluoroalkyl group-containing oligomer represented by the following general formula (2). It is characterized by being made.

{Wherein R ³ and R ⁴ represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ³ And R ⁴ may be the same group or different groups, Y in R ³ and R ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. is there. Z represents an isocyanate-containing group. m3 is an integer of 5 to 1000. The molar ratio of m1 and m2 is 1:99 to 99: 1. }

Magnetite (Fe ₃ O ₄ ) and γ-maghemite (γ-Fe ₂ O ₃ ) are preferably used as the magnetic iron oxide particles used in the first and second inventions.

  The preferred physical properties of such magnetic iron oxide particles can be used without particular limitation as long as they are nanoparticles, but in particular, according to the present invention, the magnetic iron oxide particles can be dispersed at a level of several tens of nanometers. An average particle diameter of 100 nm or less, preferably in the range of 1 to 100 nm is suitably used. The magnetic iron oxide particles may contain other iron compounds such as α-hematite and iron hydroxide as long as the effects of the present invention are not impaired.

The fluoroalkyl group-containing oligomer represented by the general formula (1) used in the first invention is a known compound and can be produced, for example, according to the following reaction formula (A-1).

(In the formula, R ¹ , R ² , B ₁ , n1, n2, and n3 are as defined above.)

  That is, the fluoroalkanoyl peroxide represented by the general formula (a1) and the sulfonic acid compound represented by the general formula (a2) and the adamantyl group-containing compound represented by (3a) are usually 1 in molar ratio. : 1 to 100: 1 to 100, preferably 1: 1 to 50: 1 to 50, 100 ° C. or lower, preferably 10 to 50 ° C. within 20 hours, preferably 2 to 5 hours. The target fluoroalkyl group-containing oligomer represented by the general formula (1) can be produced by carrying out the reaction in a solvent (for example, Langmuir, Vol. 23, No. 11, 5848-5851p (2007). )reference)

The magnetic iron oxide nanocomposite powder particles of the first invention of the present invention are one or more of the magnetic iron oxide particles represented by the general formula (1) as observed by TEM (transmission electron microscope). Included by inclusion in the alkyl group-containing oligomer, adsorbed on the surface of the fluoroalkyl group-containing oligomer particle, or present both inside and on the particle surface of the fluoroalkyl group-containing oligomer Is done.
The content of magnetic iron oxide in the magnetic iron oxide nanocomposite powdery particles is preferably 1% by weight or more, and preferably 2 to 95% by weight from the viewpoint of being applicable to various applications.

  The fluoroalkyl group-containing oligomer used in the second invention of the present invention is represented by the general formula (2). The fluoroalkyl group-containing oligomer has an isocyanate-containing group capable of cross-linking reaction. In the second invention of the present invention, the fluoroalkyl group-containing oligomer for complexing magnetic iron oxide is represented by the general formula (2). It is a crosslinking reaction product of a fluoroalkyl group-containing oligomer.

Z in the formula (2) represents an isocyanate-containing group. As the isocyanate-containing group, for example, a group represented by the following general formula (3) or (4) is preferably used.

(In the formula, B ₂ represents an alkylene group. A ₁ and A ₂ represent an alkyl group.)
The alkylene group represented by B _{2 in} the general formula (3) is preferably an alkylene group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. As the alkyl group of A ₁ and A _{2 in} the formula of the general formula (3), an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms is preferable. A ₁ and A ₂ may be different groups or the same group.

(In the formula, B ₃ represents an alkylene group.)
The alkylene group represented by B _{3 in} the formula (4) is preferably an alkylene group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.

  In the present invention, an isocyanate-containing group represented by the general formula (3) is particularly preferably used as Z in the general formula (2).

The fluoroalkyl group-containing oligomer represented by the general formula (2) is a known compound and can be produced, for example, according to the following reaction formula (A-2).

(Wherein R ³ , R ⁴ , Z, m1, m2 and m3 have the same meanings as described above.)

  That is, the fluoroalkanoyl peroxide represented by the general formula (a1) and the isocyanate group-containing compound represented by the general formula (a4) are usually in a molar ratio of usually 1: 1 to 100: 1 to 100, preferably The target is obtained by carrying out the reaction in a halogenated aliphatic solvent at 1: 1 to 50: 1 to 50 at 100 ° C. or less, preferably within 10 to 50 ° C. within 20 hours, preferably 2 to 5 hours. A fluoroalkyl group-containing oligomer represented by the general formula (2) can be produced (see, for example, JP 2007-238760 A and JP 2007-239022 A).

  The magnetic iron oxide nanocomposite powder particles according to the second invention of the present invention are, when observed with a TEM (transmission electron microscope), one or more magnetic iron oxide particles are cross-linked reaction products of the fluoroalkyl group oligomer. Included inside. The content of magnetic iron oxide in the magnetic iron oxide nanocomposite powdery particles is preferably 1% by weight or more, and preferably 2 to 95% by weight from the viewpoint of being applicable to various applications.

  In the magnetic iron oxide nanocomposite powder particles of the first and second inventions of the present invention, another preferable physical property is an average particle diameter of 10 to 990 nm, preferably 20 to 600 nm. It is preferable that the average particle diameter is in the above range in terms of good dispersibility in various dispersion solvents or resin materials.

The magnetic iron oxide nanocomposite powder particles of the first invention can be industrially advantageously produced by the following two methods.
(A) A method in which magnetic iron oxide particles and a fluoroalkyl group-containing oligomer represented by the general formula (1) are contacted in a solvent (hereinafter referred to as “Method A”).
(B) In the method of producing magnetic iron oxide by adding an alkali to a solvent containing a ferrous salt and a ferric salt and reacting, the fluoroalkyl represented by the general formula (1) is used as the solvent. A method of reacting by adding a group-containing oligomer and adding an alkali (hereinafter referred to as “Method B”).

In the contact method in the method A, for example, the magnetic iron oxide particles are added to a solution obtained by dissolving the fluoroalkyl group-containing oligomer represented by the general formula (1) in a solvent, followed by stirring and / or ultrasonic treatment. Is done.
In the method A, the magnetic iron oxide particles are easily adsorbed on the surface of the fluoroalkyl group-containing oligomer particles to be composited.

  The solvent according to Method A can dissolve the fluoroalkyl group-containing oligomer represented by the general formula (1), and a solvent inert to the fluoroalkyl group-containing oligomer and magnetic iron oxide is used. Examples thereof include lower alcohols such as methanol, ethanol and isopropyl alcohol, and among these, methanol is particularly preferable.

  The concentration of the solution in which the fluoroalkyl group-containing oligomer is dissolved in Method A is not particularly limited as long as the fluoroalkyl group-containing oligomer can be dissolved, but is usually 1 to 70% by weight, preferably 2 ~ 50% by weight.

  The amount of magnetic iron oxide added in Method A is 100 to 80000 parts by weight, preferably 200 to 70000 parts by weight, based on 100 parts by weight of the fluoroalkyl group-containing oligomer.

  The contact condition in Method A is that the contact temperature is 5 to 100 ° C, preferably 10 to 50 ° C. The contact time is 0.1 hour or longer, preferably 0.5 to 10 hours.

  After contacting for a predetermined time, the target product can be recovered from the reaction solution, and the recovered product can be dried to obtain the magnetic iron oxide nanocomposite powder particles of the first invention. In addition, as a method for recovering the target product from the reaction solution, for example, the reaction solution is centrifuged, and unreacted magnetic iron oxide is precipitated as a precipitate, the precipitate is removed from the reaction solution, and purified if necessary. The magnetic iron oxide nanocomposite powdery particles of the present invention can be obtained.

In the method B, a ferrous salt and a ferric salt are usually added to a solution obtained by dissolving the fluoroalkyl group-containing oligomer represented by the general formula (1) in a solvent, and then an alkali is added to the ferrous iron. It is carried out by conducting a hydrolysis reaction between the salt and the ferric salt.
In the method B, in TEM (transmission electron microscope) observation, one or two or more magnetic iron oxide particles are included in the fluoroalkyl group-containing oligomer represented by the general formula (1) and are combined. It is easy to obtain a composite or a composite in which magnetic iron oxide particles are present both inside and on the surface of the fluoroalkyl group-containing oligomer.

  The solvent according to Method B is not particularly limited as long as it can dissolve the fluoroalkyl group-containing oligomer represented by the general formula (1) and the ferrous salt and ferric salt, but in many cases, as the solvent Water is used.

  The concentration of the solution in which the fluoroalkyl group-containing oligomer is dissolved in Method B is not particularly limited as long as the fluoroalkyl group-containing oligomer can be dissolved, but is usually 1 to 80% by weight, preferably 5 ~ 50% by weight.

Ferrous salts include ferrous chloride (FeCl ₂ ), ferrous sulfate (FeSO ₄ ), ferrous nitrate (Fe (NO3) ₂ ), etc., and ferric chloride includes ferric chloride. Iron (FeCl ₃ ), ferric sulfate (Fe ₂ (SO ₄ ) ₃ ), ferric nitrate (Fe (NO ₃ ) ₃ ), etc. can be used, but ferrous chloride and ferric chloride are particularly Preferably used. The ferrous salt and ferric salt may be hydrated or anhydrous.

Reaction using ferrous salt and ferric salt is performed as shown in the following reaction formula (B), and magnetite is generated.
2Fe ³⁺ + Fe ²⁺ + 4OH ⁻ → FeO.Fe ₂ O ₃ + 4H ⁺ .. (B)

The addition ratio of the ferric salt of the ferrous salt is such that the ferrous ion (Fe ²⁺ ) and the ferric ion (Fe ³⁺ ) are 0.1 to 0.1 in terms of the molar ratio of both (Fe ²⁺ / Fe ³⁺ ). 10 is preferable. Moreover, the addition amount to the solution which melt | dissolved the fluoroalkyl group containing oligomer of ferrous salt and ferric salt is produced | generated with respect to 100 weight part of fluoroalkyl group containing oligomers represented by General formula (1). It is preferable to add so that the magnetite is 1 to 99 parts by weight, preferably 5 to 95 parts by weight.

  As the alkali that can be used, sodium hydroxide, potassium hydroxide, aqueous ammonia, or the like can be used. The amount of alkali added is preferably at least the reaction equivalent.

  The reaction temperature in Method B is 5 to 50 ° C., preferably 10 to 40 ° C., and the reaction time is 0.5 hours or more, preferably 0.5 to 5 hours.

  After completion of the reaction, the precipitate is recovered from the reaction solution by a conventional method, and the recovered precipitate can be dried to obtain the magnetic iron oxide nanocomposite powder particles of the first invention.

  The magnetic iron oxide nanocomposite powdery particle of the second invention is prepared by preparing a solvent containing magnetic iron oxide particles and a fluoroalkyl group-containing oligomer represented by the general formula (2), and then the general formula (2). It can manufacture by performing the crosslinking reaction of the fluoroalkyl group containing oligomer represented by these.

  Specifically, the fluoroalkyl group-containing oligomer represented by the general formula (2) is dissolved in a solvent, magnetic iron oxide is added to the solution, and then the reaction system is heated to crosslink the isocyanate group. I do.

  The solvent for dissolving the fluoroalkyl group-containing oligomer represented by the general formula (2) is not particularly limited as long as it is an inert solvent for the fluoroalkyl group-containing oligomer and magnetic iron oxide. The use of N-dimethylformamide is particularly preferred in that separation of unreacted magnetic iron oxide and product from the reaction solution is facilitated.

  The concentration of the solution in which the fluoroalkyl group-containing oligomer represented by the general formula (2) is dissolved is not particularly limited as long as the fluoroalkyl group-containing oligomer can be dissolved. 50% by weight, preferably 5 to 20% by weight.

  The amount of magnetic iron oxide added is 100 to 80000 parts by weight, preferably 200 to 70000 parts by weight, based on 100 parts by weight of the fluoroalkyl group-containing oligomer represented by the general formula (2).

  The crosslinking reaction is performed by heating. The heating temperature is 100 to 150 ° C, preferably 110 to 130 ° C, and the heating time is 0.5 hours or more, preferably 1 to 5 hours.

  After completion of the cross-linking reaction, the reaction solution is centrifuged, the unreacted magnetic iron oxide is precipitated, the solvent is then removed from the reaction solution from which the precipitate has been removed, and purification, such as recrystallization, is performed as necessary. The magnetic iron oxide nanocomposite powder particles of the second invention can be obtained.

  The magnetic iron oxide nanocomposite powder particles according to the first and second inventions of the present invention are used for magnetic materials such as magnetic tapes, high-density magnetic recording media, electromagnetic wave shielding materials, biodiagnostics, etc. It can be used suitably. In addition, magnetic iron oxide using maghemite particles effectively absorbs visible light of 600 nm. Moreover, it has characteristics such as absorbing light and showing hydrophilicity. Therefore, the magnetic iron oxide using maghemite particles can be expected for photocatalysts and solar cell electrodes.

  The magnetic iron oxide nanocomposite powdery particle dispersion of the present invention is a dispersion in which the magnetic iron oxide nanocomposite powdery particle of the present invention is dispersed in a dispersion solvent.

  The magnetic iron oxide nanocomposite powder particles of the present invention exhibit high dispersibility in various dispersion solvents. Therefore, in a dispersion obtained by dispersing the magnetic iron oxide nanocomposite powder particles of the present invention in a dispersion solvent, that is, in the magnetic iron oxide nanocomposite powder particle dispersion of the present invention, the magnetic iron oxide nanocomposite powder particles Are dispersed without agglomeration, so that no solid matter is visually observed.

  Moreover, the magnetic iron oxide nanocomposite powder-like particle dispersion of the present invention has a long dispersibility compared to the magnetic iron oxide nanocomposite powder-like particle disclosed in JP-A-2005-289794. That is, the conventional one gradually changes in the dispersion state over time, but the magnetic iron oxide nanocomposite powder-like particle dispersion of the present invention changes to the dispersion state even after at least 12 hours. Is not allowed. That is, no precipitate was observed for more than 12 hours, and the magnetic iron oxide nanocomposite powder particles were highly dispersed in the solvent, and the dispersion persistence was superior to that of the conventional one.

  In addition, the magnetic iron oxide nanocomposite powder-like particle dispersion according to the present invention is highly dispersed in a solvent even after centrifugation, with only a small amount of precipitate being observed even after centrifugation. On the other hand, when the permanent magnet is brought close to the dispersion, the precipitate is settled, and a beautiful supernatant is obtained. However, when the permanent magnet is moved away from the permanent magnet, it naturally re-disperses uniformly.

  The dispersion solvent for the magnetic iron oxide nanocomposite powder particle dispersion of the present invention is not particularly limited as long as it is inert and can be uniformly dispersed in the magnetic iron oxide nanocomposite powder particle of the present invention. Alternatively, any organic solvent may be used, and the organic solvent may be either a polar organic solvent or a nonpolar organic solvent. Examples of the organic solvent according to the magnetic iron oxide nanocomposite powder particle dispersion of the present invention include methanol, ethanol, dimethyl sulfoxide, dimethylformamide, tert-butyl alcohol, water, and the like. The magnetic iron oxide nanocomposite powder particles of the invention exhibit extremely high dispersibility in water, methanol, dimethyl sulfoxide, dimethylformamide, and tert-butyl alcohol. The magnetic iron oxide nanocomposite powder particles of the second invention of the present invention exhibit extremely high dispersibility in methanol.

  The concentration of the magnetic iron oxide in the magnetic iron oxide nanocomposite powder dispersion of the present invention is not particularly limited as long as it is appropriately adjusted in consideration of the application and usage method. 1 to 90% by weight.

  The resin composition of the present invention contains the magnetic iron oxide nanocomposite powder particles of the present invention. In other words, in the resin composition of the present invention, the magnetic iron oxide nanocomposite powder particles of the present invention are dispersed in a resin material. Since the magnetic iron oxide nanocomposite powder particles of the present invention are fine and highly dispersible in the resin material, the resin composition of the present invention has fine and uniform magnetic iron oxide nanocomposite powder particles. It is the resin composition disperse | distributed to.

  In the resin composition of the present invention, the resin material in which the magnetic iron oxide nanocomposite powder particles are dispersed is not particularly limited. When used as a rubber composition, for example, natural rubber, styrene-butadiene rubber (SBR) is used. ), Acrylonitrile-butadiene rubber (NBR), butyl rubber (IIR), polybutadiene rubber (BR), ethylene-propylene rubber (EPPM), chlorobutylene rubber (CR), polyisobutylene rubber, allyl rubber, hydrogenated acrylonitrile- Examples thereof include butadiene rubber, polysulfide rubber, urethane rubber, chlorinated sulfonated rubber, silicone rubber, and modified products thereof, and these may be two or more kinds of blend rubbers. In addition, as resins used as a matrix when obtaining resin molded products such as sheets, films, containers, fibers, etc., for example, polyvinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polycarbonate resin, polyester resin, polystyrene resin , ABS resin, AS resin, thermoplastic resin such as thermoplastic acrylic resin, epoxy resin, unsaturated polyester resin, diaryl phthalate resin, phenol resin, thermosetting resin such as urea resin, alkyd resin, melanin resin, guanazine resin, Examples thereof include vinyl resins, epoxy resins, polyamine resins, acrylic resins, polybutadiene resins, urethane resins, silicon resins, fluorine-containing resins, and modified products thereof.

  In the resin composition of the present invention, the content of the powdered magnetic iron oxide nanocomposite particles of the present invention is usually 0.01 to 50% by weight, preferably 0.5 to 50% by weight.

  In addition, the resin composition of the present invention includes, as other components, organic fillers such as white carbon, carbon black, zeolite, calcium carbonate, clay, barium sulfate, and magnesium carbonate, high styrene resin, lignin, phenol resin, and the like. Known in such fields as fillers, antibacterial agents, ultraviolet absorbers, antioxidants, extenders, dispersion aids, vulcanizing agents, vulcanization accelerators, vulcanization aids, softeners, anti-aging agents, plasticizers, etc. The additive may be contained.

  The resin composition of the present invention is obtained by, for example, mixing the magnetic iron oxide nanocomposite powder particles of the present invention with a desired resin material, melt blending, and the like, thereby adding the magnetic iron oxide nanocomposite of the present invention to the resin material. Manufactured by dispersing powder particles. The resin composition of the present invention is, for example, a magnetic iron oxide nanocomposite powder particle of the present invention or a magnetic iron oxide nanocomposite powder particle dispersion of the present invention in a resin solution in which a desired resin material is dissolved in a solvent. After the liquid is added and mixed, for example, it is formed into a desired shape such as a film, dried, and evaporated to remove the solvent.

  The resin composition containing magnetic iron oxide nanocomposite powder particles according to the present invention has water and oil repellency and can be suitably used particularly for applications such as electromagnetic wave shielding.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.

<Preparation of oligomer containing fluoroalkyl group>
(Synthesis of fluoroalkyl group-containing oligomer represented by the general formula (1) (hereinafter also referred to as “Rf-AMPS oligomer”))
(Synthesis Example A1)
In the fluorine-based solvent AK-225 (trade name: Asahi Clin AK-225 manufactured by Asahi Glass Co., Ltd.), the initiator: fluoroalkanoyl peroxide (R ^F CO ₂ ) ₂ [R ^F : —CF (CF ₃ ) OC ₃ F ₇ ] Of 2.acrylamido-2-methylpropanesulfonic acid and 17.7 mmol of 3-hydroxy-1-adamantyl acrylate were stirred at 45 ° C. for 5 hours under nitrogen, Reaction was performed. After the reaction, the mixture was centrifuged to remove unreacted monomers, washed with AK-225 several times, and further centrifuged to collect the reaction product. The obtained reaction product was dried with a vacuum dryer for 1 day to obtain the target oligomer.
The copolymerization ratio (molar ratio) obtained by ¹ H-NMR of the obtained oligomer was n1: n2 = 11: 89.
The molecular weight was measured by size exclusion chromatography (SEC) (DS-4 manufactured by Shodex), but the number average molecular weight Mn was not measurable.

(Synthesis Examples A2 to A6)
The target oligomer was obtained by the same reaction operation as in Synthesis Example A1, except that the charged molar ratio of each raw material was changed.

(Synthesis Example 2; fluoroalkyl group-containing oligomer represented by the general formula (2) (hereinafter sometimes abbreviated as “Rf-IEM oligomer”))
In the fluorine-based solvent AK-225 (trade name: Asahi Clin AK-225 manufactured by Asahi Glass Co., Ltd.), the initiator: fluoroalkanoyl peroxide (R ^F CO ₂ ) ₂ [R ^F : —CF (CF ₃ ) OC ₃ F ₇ ] 11.9 mol of 2-([1′-methylpropylideneamino] carboxyamino) ethyl acrylate and 11.9 mmol of 3-hydroxy-1-adamantyl acrylate under nitrogen. The reaction was conducted by stirring at 45 ° C. for 5 hours. After the reaction, the mixture was centrifuged to remove unreacted monomers, washed with AK-225 several times, and further centrifuged to collect the reaction product. The obtained reaction product was dried in a vacuum dryer for 1 day to obtain 15.1 g of the target oligomer. The yield was 58%.
The copolymerization ratio (molar ratio) obtained by ¹ H-NMR of the obtained oligomer was m1: m2 = 21: 79.
The molecular weight was measured by size exclusion chromatography (SEC) (DS-4 manufactured by Shodex). The number average molecular weight Mn was 9130, and the molecular weight distribution (Mw / Mn) was 1.85.

(Magnetic iron oxide)
The following commercially available magnetic iron oxide particles were used in the examples. The average particle diameter is a value obtained by a laser light scattering method.
(1) Magnetite (Fe ₃ O ₄ ); average particle size 10 nm, manufactured by Toda Kogyo Co., Ltd. (2) Maghemite (Fe ₂ O ₃ ); average particle size 50 nm, manufactured by Toda Kogyo Co., Ltd.

{Examples 1-6}
Using N, N-dimethylformamide as a solvent, 1 g of the fluoroalkyl group-containing oligomer sample (B1) prepared above, magnetite particles were added at the ratio shown in Table 3, and the mixture was irradiated with ultrasonic waves for 2 days. Subsequently, the crosslinking reaction was performed at 130 degreeC for 1 hour. After completion of the reaction, unreacted magnetite particles were removed from the reaction solution by centrifugation. Next, after concentrating the reaction solution to obtain a residue, the obtained residue is reprecipitated with acetone, decanted, and dried in a vacuum drier for 1 day to obtain a magnetic iron oxide nanocomposite powder particle sample. It was.
As a result of analyzing the obtained magnetic iron oxide nanocomposite powdery particle sample by IR, a peak due to the cross-linked product of the fluoroalkyl group-containing oligomer sample (B1) was observed in all examples (see FIG. 1). ). Further, as a result of X-ray diffraction analysis of the obtained magnetic iron oxide nanocomposite powdery particle sample, a peak derived from Fe ₃ O ₄ was observed (see FIGS. 2 and 3).
Moreover, it was confirmed by TEM observation that the magnetite particles were taken into the crosslinked product of the fluoroalkyl group-containing oligomer sample (B1) and the magnetite particles were encapsulated. A TEM photograph of the magnetic iron oxide nanocomposite powder particle sample obtained in Example 2 is shown in FIG.

Note) Yield is based on fluoroalkyl group-containing oligomer and magnetite.

<Physical property evaluation>
About the magnetic iron oxide nanocomposite powdery particle sample obtained in Examples 1 to 6, the content of magnetite particles and the average particle diameter were evaluated.

(Evaluation of magnetite particle content)
The obtained magnetic iron oxide nanocomposite powder particles were subjected to TGA measurement. The content of magnetite particles was determined from the TGA curve.

(Evaluation of average particle size)
The obtained magnetic iron oxide nanocomposite powder particles were redispersed in methanol and measured using a light scattering photometer (DLS-6000HL manufactured by Otsuka Electronics).

(Evaluation of dispersibility in solvent)
(Evaluation 1);
The dispersibility of the obtained magnetic iron oxide nanocomposite powder particles in each dispersion solvent was tested. The results are shown in Table 5. For evaluation, 0.01 g of magnetic iron oxide nanocomposite powder particles were added to 5 ml of a solvent, and the dispersion state was visually observed. The evaluation is shown in Table 5.
In addition, the symbol in a table | surface shows the following.
×: Not dispersed △; Partially dispersed ○; Completely dispersed ◎; Good dispersed

_{Note) AK-225 (Cl 2 CHCF} 2 CF 3 and CClF ₂ CF ₂ CHClF the weight ratio of 1: mixed solvent of 1), DE (1,2-dichloroethane), THF (tetrahydrofuran), DMSO (dimethylsulfoxide), DMF (dimethylformamide)

(Evaluation 2);
Using the magnetic iron oxide nanocomposite powder particles obtained in Examples 1 to 3, a particle dispersion was prepared by dispersing the magnetic iron oxide nanocomposite powder particles in methanol at a concentration of 0.174 g / dm ^3. did. The obtained dispersion was measured for changes in light transmittance and turbidity with time of absorbance at 500 nm of the dispersion after dispersion in a thermostatic bath at 30 ° C. The results are shown in FIGS.
From the results of FIGS. 5 and 6, there is no change in light transmittance and turbidity even after 12 hours have elapsed, compared to the time of dispersion. Therefore, it can be seen that the magnetic iron oxide nanocomposite powder-like particles of the present invention are particles that can be persistently dispersed and have extremely high dispersibility.

(Evaluation 3);
Using the magnetic iron oxide nanocomposite powdery particles obtained in Example 3 and Example 6, a particle dispersion obtained by dispersing the magnetic iron oxide nanocomposite powdery particles in methanol at a concentration of 0.02 g / L. Prepared. The obtained dispersion was centrifuged at 800 G for 30 minutes and at 800 G for 60 minutes, and the dispersion state before and after the centrifugation was visually observed. In any of the examples, the magnetic iron oxide nanocomposite powder particles were highly dispersed even after the centrifugation process, so that only a slight precipitate could be confirmed after the centrifugation.

(Evaluation 4);
Particles obtained by dispersing the magnetic iron oxide nanocomposite powder particles in methanol at a concentration of 0.02 g / L in a sample bottle using the magnetic iron oxide nanocomposite powder particles obtained in Example 3 and Example 6. A dispersion was prepared. When a permanent magnet was placed on the bottom of the sample bottle, the precipitate settled. Furthermore, as soon as the permanent magnet was removed from the bottom of the sample bottle, the precipitate redispersed.

(Resin composition)
(Evaluation 1);
The magnetic iron oxide nanocomposite powder particles obtained in Examples 1, 4 and 5 were dispersed in 5 ml of methanol to prepare a dispersion. Separately, a solution in which 0.99 g of polymethyl methacrylate resin (PMMA) was dissolved in 20 ml of dichloroethane was prepared. Next, the solution and the dispersion were mixed, and a 1% PMMA modified film (containing 10 mg of nanocomposite particles) and a 3% PMMA modified film (containing 30 mg of nanocomposite particles) were prepared by a casting method. The contact angles at room temperature (25 ° C.) of dodecane on the front and back surfaces of the obtained film were measured.
Moreover, when a permanent magnet was brought close to the obtained 3% PMMA modified film (containing 30 mg of nanocomposite particles), the PMMA modified film was attracted to the magnet.

(Evaluation 2);
The magnetic iron oxide nanocomposite powder particles obtained in Examples 1 to 6 were prepared in the same manner as in Evaluation 1 above to prepare a 3% PMMA modified film (containing 30 mg of nanocomposite particles), and the front and back surfaces of the obtained films The contact angle of dodecane and water at room temperature (25 ° C.) was measured.

{Example 7}
In 15 ml of methanol, 150 mg of a fluoroalkyl group-containing oligomer sample (A3) and 15 mg of magnetite particles were placed and irradiated with ultrasonic waves at room temperature (25 ° C.) for 6 hours. Next, the unreacted magnetite particles were removed from the reaction solution by centrifugation. Next, the reaction solution was concentrated to obtain a residue, which was then dried in a vacuum dryer for 1 day to obtain a magnetic iron oxide nanocomposite powdery particle sample (yield 68%).
As a result of analyzing the obtained magnetic iron oxide nanocomposite powdery particle sample by IR, a peak attributable to the fluoroalkyl group-containing oligomer sample (A3) was observed. Further, as a result of X-ray diffraction analysis of the obtained magnetic iron oxide nanocomposite powdery particle sample, a peak derived from Fe ₃ O ₄ was observed.
Moreover, it was confirmed by TEM observation that magnetite particles were present on the particle surface of the fluoroalkyl group-containing oligomer particles and were combined.

{Example 8}
In 15 ml of methanol, 150 mg of a fluoroalkyl group-containing oligomer sample (A3) and 15 mg of maghemite particles were placed and irradiated with ultrasonic waves at room temperature (25 ° C.) for 6 hours. Subsequently, the unreacted maghemite particles were removed from the reaction solution by centrifugation. Next, the reaction solution was concentrated to obtain a residue, which was then dried in a vacuum dryer for 1 day to obtain a magnetic iron oxide nanocomposite powdery particle sample (yield 68%).
As a result of analyzing the obtained magnetic iron oxide nanocomposite powdery particle sample by IR, a peak attributable to the fluoroalkyl group-containing oligomer sample (A3) was observed. Further, as a result of X-ray diffraction analysis of the obtained magnetic iron oxide nanocomposite powdery particle sample, a peak derived from Fe ₂ O ₃ was observed.
Moreover, it was confirmed by TEM observation that magnetite particles were present on the particle surface of the fluoroalkyl group-containing oligomer particles and were combined.

<Physical property evaluation>
About the magnetic iron oxide nanocomposite powder-form particle sample obtained in Examples 7-8, it carried out similarly to Examples 1-6, and evaluated about content of a magnetite particle or a maghemite particle | grain, and an average particle diameter.

<Evaluation of dispersibility in solvent>
Using the magnetic iron oxide nanocomposite powdery particle sample obtained in Example 7, a particle dispersion was prepared by dispersing the magnetic iron oxide nanocomposite powdery particle in t-butyl alcohol at a concentration of 4 g / L. . The obtained dispersion was subjected to dynamic light scattering measurement while raising the temperature. The results are shown in Table 9.

From the results in Table 7, it can be seen that the magnetic iron oxide nanocomposite powder particles of the present invention maintain a stable dispersion state in a temperature range of at least 30 to 70 ° C.

{Examples 9 to 21}
40 mg of a fluoroalkyl group-containing oligomer sample was added to 20 ml of water, and the mixture was stirred overnight at room temperature (25 ° C.) using a magnetic stirrer. Then, iron (II) chloride tetrahydrate and iron (III) chloride hexahydrate were added and irradiated with ultrasonic waves for 30 minutes. Next, 25% aqueous ammonia was added, and the reaction was performed at room temperature (25 ° C.) for 6 hours. Table 9 shows the raw material charge and yield.
After the reaction was completed, the precipitate was collected by filtration, and the collected product was dried for 1 day with a vacuum dryer to obtain a magnetic iron oxide nanocomposite powder particle sample.
As a result of analyzing the obtained magnetic iron oxide nanocomposite powdery particle sample by IR, a peak attributed to a fluoroalkyl group-containing oligomer sample (Rf-AMPS oligomer) was observed in all examples (see FIG. 7). . Further, as a result of X-ray diffraction analysis of the obtained magnetic iron oxide nanocomposite powdery particle sample, a peak derived from Fe ₃ O ₄ was observed (see FIG. 8).
Moreover, it was confirmed by TEM observation that the maghemite particles were taken into the fluoroalkyl group-containing oligomer sample and the maghemite particles were encapsulated. FIG. 9 shows a TEM photograph of the magnetic iron oxide nanocomposite powder particle sample obtained in Example 14.

(Evaluation of the physical properties)
About the obtained magnetic iron oxide nanocomposite powder-like particle sample, it carried out similarly to Examples 1-6, and evaluated about content, average particle diameter, and zeta potential of a magnetite particle.
In addition, about the measurement of an average particle diameter, water and methanol were used as a dispersion medium. The zeta potential was measured using a particle dispersion (pH 7) in which the obtained magnetic iron oxide nanocomposite powder particles were dispersed in water at a concentration of 0.01 g / L.

(Evaluation of dispersibility in solvent)
(Evaluation 1);
The dispersibility of the magnetic iron oxide nanocomposite powder particles obtained in Examples 11, 15, 16, and 19 in each dispersion solvent was tested. The results are shown in Table 10. For evaluation, 0.01 g of magnetic iron oxide nanocomposite powder particles were added to 5 ml of a solvent, and the dispersion state was visually observed.
In addition, the symbol in a table | surface shows the following.
×: Not dispersed △; Partially dispersed ○; Completely dispersed ◎; Good dispersed

_{Note) AK-225 (Cl 2 CHCF} 2 CF 3 and CClF ₂ CF ₂ CHClF the weight ratio of 1: mixed solvent of 1), DE (1,2-dichloroethane), THF (tetrahydrofuran), DMSO (dimethylsulfoxide), DMF (dimethylformamide)

(Evaluation 2);
Using the magnetic iron oxide nanocomposite powdery particles obtained in Example 19, a particle dispersion was prepared by dispersing the magnetic iron oxide nanocomposite powdery particles in methanol at a concentration of 0.02 g / L. The obtained dispersion was centrifuged at 800 G for 30 minutes and 800 G for 1 hour, and the dispersion state before and after the centrifugation was visually observed. In any of the examples, the magnetic iron oxide nanocomposite powder particles were highly dispersed even after the centrifugation process, so that only a slight precipitate could be confirmed after the centrifugation.

(Evaluation 3);
Using the magnetic iron oxide nanocomposite powdery particles obtained in Example 19, a particle dispersion was prepared by dispersing the magnetic iron oxide nanocomposite powdery particles in methanol at a concentration of 0.02 g / L in a sample bottle. did. When a permanent magnet was placed on the bottom of the sample bottle, the precipitate settled. Furthermore, as soon as the permanent magnet was removed from the bottom of the sample bottle, the precipitate redispersed.

{Examples 22 to 27}
In 15 ml of methanol, 150 mg of a fluoroalkyl group-containing oligomer sample (A3) and the amount of magnetite particles shown in Table 13 were placed, and ultrasonic waves were irradiated at room temperature (20 ° C.) for 6 hours. Next, the unreacted magnetite particles were removed from the reaction solution by centrifugation. Next, the reaction solution was concentrated to obtain a residue, and then dried in a vacuum dryer for 1 day to obtain a magnetic iron oxide nanocomposite powder particle sample.
As a result of analyzing the obtained magnetic iron oxide nanocomposite powdery particle sample by IR, a peak attributable to the fluoroalkyl group-containing oligomer sample (A3) was observed. Further, as a result of X-ray diffraction analysis of the obtained magnetic iron oxide nanocomposite powdery particle sample, a peak derived from Fe ₃ O ₄ was observed.
Moreover, it was confirmed by TEM observation that magnetite particles were present on the particle surface of the fluoroalkyl group-containing oligomer particles and were combined. FIG. 10 shows a TEM photograph of the magnetic iron oxide nanocomposite powder particle sample obtained in Example 22.

<Physical property evaluation>
About the magnetic iron oxide nanocomposite powder-like particle sample obtained in Examples 22 to 27, the content of magnetite particles and the average particle diameter were evaluated in the same manner as in Examples 1 to 6.

<Evaluation of dispersibility in solvent>
Using the magnetic iron oxide nanocomposite powder particles obtained in the examples, a particle dispersion was prepared by dispersing the magnetic iron oxide nanocomposite powder particles in t-butyl alcohol at a concentration of 4 g / L. The lower critical solution temperature (also referred to as “LCST”) was measured by the method described below, and dynamic light scattering measurement was performed while raising the temperature of the obtained dispersion. The results are shown in Table 15.
(Evaluation of lower critical solution temperature (LCST))
Using the magnetic iron oxide nanocomposite powder particles obtained in Examples 22, 23, 25, 26 and 27, the magnetic iron oxide nanocomposite powder particles were dispersed in t-butyl alcohol at a concentration of 4 g / L. A particle dispersion was prepared.
Next, the light transmittance was measured at a wavelength of 500 nm while raising the temperature, and when the light transmittance was 100 at 30 ° C., the temperature at which the light transmittance was 50% was defined as the lower critical solution temperature (LCST). In addition, in the case of what was added to t-butyl alcohol by the density | concentration of Rf-AMPS oligomer 4g / L (blank), the lower critical solution temperature (LCST) was 78 degreeC.

Note) "-" indicates that no measurement is performed.

  According to the present invention, it is possible to provide magnetic iron oxide nanocomposite powder-like particles having extremely high dispersibility of several tens of nanometers in various solvents and having a long dispersibility. In addition, according to the present invention, the magnetic iron oxide nanocomposite powder particles can be provided by an industrially advantageous method.

Claims (10)

Magnetic iron oxide nanocomposite powdery particles, wherein magnetic iron oxide particles are composited with a fluoroalkyl group-containing oligomer represented by the following general formula (1).

{In the formula, R ¹ and R ² represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ¹ And R ² may be the same group or different groups, Y in R ¹ and R ² represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. is there. B ₁ represents an alkylene group having 1 to 5 carbon atoms. n3 is an integer of 5 to 1000. The molar ratio of n1 and n2 is 1:99 to 99: 1. } Magnetic iron oxide nanocomposite powder-like particles, wherein magnetic iron oxide particles are composited with a crosslinking reaction product of a fluoroalkyl group-containing oligomer represented by the following general formula (2).

{Wherein R ³ and R ⁴ represent a — (CF ₂ ) p—Y group or a —CF (CF ₃ ) — [OCF ₂ CF (CF ₃ )] q—OC ₃ F ₇ group, and R ³ And R ⁴ may be the same group or different groups, Y in R ³ and R ⁴ represents a hydrogen atom, a fluorine atom or a chlorine atom, and p and q are integers of 0 to 10. is there. Z represents an isocyanate-containing group. m3 is an integer of 5 to 1000. The molar ratio of m1 and m2 is 1:99 to 99: 1. } A powdered magnetic iron oxide composite powder particle, wherein Z in the formula of the fluoroalkyl group-containing oligomer represented by the general formula (2) is a group represented by the following general formula (3).

(In the formula, B ₂ represents an alkylene group. A ₁ and A ₂ represent an alkyl group.)   3. The magnetic iron oxide nanocomposite powder particles according to claim 1 or 2, wherein the average particle size is 10 to 900 nm.   The magnetic iron oxide nanocomposite powder particles according to claim 1 or 2, wherein the magnetic iron oxide particles are magnetite particles or maghemite particles.   The method for producing magnetic iron oxide nanocomposite powder particles according to claim 1, wherein the magnetic iron oxide particles and the fluoroalkyl group-containing oligomer represented by the general formula (1) are contacted in a solvent.   In the method for producing magnetic iron oxide by adding an alkali to a solvent containing a ferrous salt and a ferric salt and performing a reaction, the fluoroalkyl group-containing oligomer represented by the general formula (1) is used as the solvent 2. The method for producing magnetic iron oxide nanocomposite powder particles according to claim 1, wherein the reaction is carried out by adding an alkali.   Preparing a solvent containing magnetic iron oxide particles and a fluoroalkyl group-containing oligomer represented by the general formula (2), and then performing a crosslinking reaction of the fluoroalkyl group-containing oligomer represented by the general formula (2). 3. The method for producing magnetic iron oxide nanocomposite powder particles according to claim 2.   6. A particle dispersion liquid, wherein the magnetic iron oxide nanocomposite powder particles according to any one of claims 1 to 5 are dispersed in a dispersion solvent.   A resin composition comprising the magnetic iron oxide nanocomposite powder particles according to any one of claims 1 to 5.