JP5481653B2 - Nanocomposite, nanodispersion, method for producing the same, and various agents comprising the dispersion - Google Patents

Description

  The present invention relates to a nanocomposite containing a fluorine-containing compound and a silane coupling agent, a nanodispersion, a production method thereof, and various agents comprising the dispersion.

  From the viewpoint of environmental problems in recent years, it is necessary to wash away with a detergent if it gets dirty, and as a coating agent for various substrates such as glass, water repellent, hydrophilic Antifouling agents having an oil effect have been researched and developed (see, for example, Patent Documents 1 and 2). Since these coating agents are nanomaterials, nanocomposites, or nanodispersions, they can exhibit various functions, and are particularly excellent in solution dispersibility, and when coated on various substrates, they are excellent in transparency and impair the appearance. There is nothing. By coating a transparent substrate such as glass, problems such as unevenness, cloudiness, and opacity can be solved.

JP2007-99793 JP2008-40171

  Under such circumstances, it is an object of the present invention to provide novel nanocomposites and nanodispersions, particularly those having excellent water / oil repellency and hydrophilic / oil repellency.

  As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a fluorine-containing compound having a fluorine-containing terminal chain group and having a specific amphiphilic group in the main chain skeleton itself forms a molecular assembly. It has been found that nanomaterials can be formed, and that this fluorine-containing compound can form a composite with a silane coupling agent. Furthermore, these nanomaterials and composites are nano-sized particles and contain fluorine-containing compounds. It is amphiphilic in aqueous solvents, non-aqueous solvents, hydrophobic solvents, or mixed solvents that follow the amphipathic properties of these compounds, and these nanoparticles can be dispersed in these solvents. The inventors have found that the hard surface can be modified with a liquid, and that the surface can be modified by addition to a paint or resin, and the present invention has been made based on these findings.

That is, the present invention is as follows.
(1) General formula (I)
[Wherein Rf is a perfluoroalkyl group, a perfluorooxaalkyl group or a general formula
(In the formula, Af is a perfluoroalkylene group, Af ′ is the same or different perfluoroalkylene group as Af, and m is 1 to 10).
R is an alkyl group, an alkoxyalkyl group or a hydrogen atom, and n is 2 to 100. ]
And a fluorine-containing compound represented by the general formula (III)
[Wherein X is selected from the group consisting of vinyl group, styryl group, methacryloxy group, acryloxy group, amino group, quaternary ammonium group, ureido group, sulfide group, isocyanate group, alkoxy group, sulfo group and phosphate group. A is a divalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom or a sulfur atom, R ¹ is a hydroxyl group, R ² is an alkyl group, an alkoxyalkyl group or hydrogen An atom and m is 1 or 2; ]
A nanocomposite comprising a silane coupling agent represented by:
(2) The fluorine-containing compound is represented by the formula (II)
[Wherein, R _F is represented by — (CF ₂ ) pF or —CF (CF ₃ ) O (CF ₂ CFCF ₃ O) qC ₃ F ₇ (p is 1 to 10, q is 0 to 5). Group, R 'is an alkyl group, n is 2-3. ]
The nanocomposite as described in (1) above, which is represented by:
(3) A nano-dispersed liquid obtained by dispersing the nano-composite according to (1) or (2) in a solvent.
(4) The nanodispersion according to (3), wherein the solvent is a non-aqueous solvent or a hydrophobic solvent.
(5) The (3) or (4), wherein the fluorine-containing compound according to (1) or (2) and the silane coupling agent according to (1) are mixed in a solvent. A method for producing the nano-dispersion described in 1.
(6) A coating agent comprising the nanodispersion according to (3) or (4).
(7) An additive comprising the nanodispersion according to (3) or (4).

Hereinafter, the present invention will be specifically described.
The nanocomposite of the present invention comprises a nanoparticle composite of the fluorine-containing compound of the above formula (I) and the silane coupling agent of the above formula (III), and preferably comprises only the nanoparticle composite. It is.

In formula (I), the alkyl group of R is preferably a methyl group or an ethyl group, and n is preferably 1-20. As for the Rf group, examples of the perfluoroalkyl group include such as _{C 3 F 7, C 6 F} 13, C 7 F 15, -CF (CF 3) Examples of perfluoroalkyl oxaalkyl group OC ₃ F ₇ is mentioned, Rf groups at both terminals may be different from each other, and Rf groups may be different between molecules.
As the fluorine-containing compound, those represented by the above formula (II) are particularly preferable. Specifically, fluoroalkyl group is particularly preferably groups represented by _{-CF (CF 3) OC 3 F} 7 represented by _{R F,} groups represented by R are methyl groups, i.e. -Si _{(OCH 3)} 3 Is particularly preferred.

The production method of the fluorine-containing compound is not particularly limited, but preferably, a method of reacting an olefin monomer corresponding to the target product in the presence of the organic peroxide containing the Rf group, for example, the peroxide is a radical. As a polymerization initiator, the polymerization or copolymerization reaction of the monomer may be used.
As the organic peroxide containing an Rf group, a peroxide having a corresponding Rf group at both ends as exemplified above is preferable, and such a peroxide is represented by Rf—CO—OO—OC—Rf. And the compounds shown (wherein the Rf groups may be the same as or different from each other).
The fluorine-containing compound may include a compound in which the Rf group is introduced at all ends together with a compound in which the Rf group is introduced only at one end, and further a group derived from a solvent or the like by radical chain transfer. Or a group derived from a radical termination reaction by a disproportionation reaction may be included at one end.

  The silane coupling agent of formula (III) is vinyl group, styryl group, methacryloxy group, acryloxy group, amino group, quaternary ammonium group, ureido group, sulfide group, isocyanate group, alkoxy group, sulfo group, phosphate group A silane coupling agent having a functional group selected from the group consisting of, for example, a sulfonic acid group as shown in the following chemical formula is preferable.

Formula (IV)

  The nanocomposite of the present invention usually has an average particle size of several nm to several hundred nm, preferably 10 to 500 nm, and can be dispersed as nanoparticles in various solvents, thus preparing a nano-dispersed liquid Yes.

The nanocomposite of the present invention can be produced as follows.
The nanocomposite of the present invention is prepared by mixing a fluorine-containing compound of the above formula (I) and a silane coupling agent of the above formula (III) in a solvent under acidic or alkaline conditions to prepare a nanodispersion, It can be obtained by removing the solvent from the liquid.
As a solvent used in this production method, a mixed solvent of water and an organic solvent is preferable, and such a solvent is acidified with an acid such as acetic acid, hydrochloric acid, sulfuric acid, nitric acid, etc., and an inorganic such as ammonia, sodium hydroxide or the like. The pH is adjusted to be alkaline with an organic base such as a base, triethylamine, or triethanolamine, and the organic solvent is preferably an alcohol solvent such as methanol, ethanol, or propyl alcohol, a glycol solvent such as ethylene glycol or propylene glycol, tetrahydrofuran, Hydrophilic solvents such as dioxane, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, and 3-methoxy-3-methylbutanol can be mentioned. In terms of operability and safety, hydrochloric acid and aqueous ammonia are used as organic solvents for pH adjustment. Is isopropyl alcohol Preferably used Le.
In addition, since the silane coupling agent of the said Formula (III) itself shows acidity, in the case of mixing under acidic condition, it is not necessary to use the said acid.
The pH of the solvent is preferably 1 to 6 on the acidic side, preferably 8 to 14 on the alkaline side, and more preferably 2 to 4 and 9 to 12.
The mixing ratio of water and organic solvent can be arbitrarily changed, but water: organic solvent = 0.1: 9.9 to 5: 5 is preferable, and considering the solubility of the fluorine-containing compound, water: organic solvent = 1: 9 to 3: 7 (w / w) is more preferable.
The mixing ratio of the fluorine-containing compound and the silane coupling agent can be arbitrarily determined. In order to exhibit the desired oil repellency and hydrophilicity, the silane coupling agent is preferably 2 to 100 times the weight of the fluorine-containing compound. 10 to 10 times is more preferable.
Mixing is usually carried out at a temperature from 5 ° C. to near the boiling point below the boiling point of the solvent, preferably at ordinary temperature and normal pressure.
In order to remove the solvent from the nano-dispersion, for example, the solvent may be distilled off or evaporated.
The nano-dispersion of the present invention can be obtained by stopping the process up to the stage before the final step of removing the solvent in the above-described method for producing a nano-composite, and can also be prepared by dispersing the nano-composite in a solvent.

  The nano-dispersed liquid can be applied to a hard surface and dried to form a film on the surface, and by adding to a paint or resin, the nano-material or nano-composite is oriented on the dry surface. This film has a large contact angle with organic media such as dodecane and exhibits oil repellency, and the contact angle with water can be controlled by selecting an object to be composited. Showing gender. Since these antifouling properties are exhibited, the nano-dispersed liquid can be used as a water / oil repellent, an antifouling agent, a coating agent, an additive, and the like.

The nanocomposite of the present invention has excellent dispersibility and can be used as a dispersion dispersed in an organic solvent. This dispersion has a high contact angle with higher hydrocarbons such as dodecane and exhibits oil repellency. The contact angle to water can be controlled by selecting the object to be composited, and it exhibits water repellency and hydrophilicity.
The nano dispersion liquid of the present invention can impart water repellency / oil repellency, hydrophilicity / oil repellency to a hard surface such as glass, metal, ceramics, plastic, a coated plate of a vehicle body, etc., and exhibits a high antifouling effect. It can be used as a coating agent. In addition, by adding to paints and resins, nanomaterials or nanocomposites can be oriented on the dry surface, thus imparting water and oil repellency, hydrophilic and oil repellency to the dried coating film and resin surface. It can be used as an additive or the like showing a high antifouling effect.

The measurement photograph (after shrinkage | contraction) of the water contact angle by the expansion / contraction method with respect to the glass coated with the nanocomposite dispersion liquid obtained in Example 4. FIG. The photograph of the contact angle of water measured by the expansion / contraction method on the glass coated with the nanocomposite dispersion obtained in Comparative Example 4 (after contraction).

Next, modes for carrying out the present invention will be described by way of examples, but the present invention is not limited to these examples.
In addition, the average particle diameter in an Example and a comparative example was measured using the dynamic light-scattering photometer ("DLS-7000H" by Otsuka Electronics Co., Ltd.).

Fluorine-containing compound [in the above formula (II), a compound in which Rf = CF (CF ₃ ) OC ₃ F ₇ , n = 2 is dissolved in a mixed solvent of isopropanol and water so as to be 0.1 (wt)% The mixture was stirred at room temperature for 1 day to obtain a transparent dispersion of nanomaterials. The mixed solvent is isopropanol: water = 8: 2 (w / w).

  In Example 1, the mixed solvent water was replaced with water adjusted to pH 2 with 0.1N hydrochloric acid, and the same operation was performed.

  In Example 1, the same operation was performed by replacing the mixed solvent water with water adjusted to pH 10 with 28% aqueous ammonia.

(Comparative Examples 1-3)
In Examples 1 to 3, the same operation was performed by replacing the fluorinated compound with trifluoropropyltrimethoxysilane.

<Contact angle measurement>
The transparent dispersions of the above Examples and Comparative Examples were prepared by dip-treating a preparation (76 mm × 26 mm) whose surface was degreased with isopropanol, followed by drying at room temperature for 1 day, and the contact angles for water and dodecane were determined by Kyowa Interface Science Co., Ltd. The DM700 type fully automatic contact angle meter.
The measurement results are shown in Table 1.

<Average particle size measurement>
In Examples 1 to 3, the average particle size of fine particles in the transparent dispersion was measured by a dynamic light scattering method. As a result, the average particle size was about 180 to 670 nm, and the production of nanoparticles of the fluorine-containing compound was confirmed.

0.02 g of a fluorine-containing compound [compound in which Rf = CF (CF ₃ ) OC ₃ F ₇ , n = 2 in the above formula (II)] is dissolved in 2 ml of isopropanol, and then a silane coupling agent [the above formula In (III), X is SO ₃ H, A is C ₃ H ₆ , R ¹ is OH, R ² is H, and m is 1] 0.18 g is dissolved and stirred at room temperature for 1 day A transparent dispersion of nanocomposites was obtained.
A photograph (after shrinkage) of the contact angle of water by the expansion / shrinkage method on the glass coated with the nanocomposite dispersion is shown in FIG.
From this, it can be seen that when a water droplet is once created on the surface of the base material and water is sucked up from the syringe, the surface of the base material is hydrophilic, and therefore the surface is wet.

(Comparative Example 4)
In Example 4, the same operation was performed by replacing the added amount of the silane coupling agent with isopropanol.
A measurement photograph (after shrinkage) of the contact angle of water by the expansion / shrinkage method for the glass coated with the obtained dispersion is shown in FIG.
From this, it can be seen that since the surface of the base material is water repellent, the surface is not wet even when water is sucked up from the syringe.

<Contact angle measurement>
The transparent dispersions of the above examples and comparative examples were dip-treated with a preparation (76 mm × 26 mm) whose surface was degreased with isopropanol, dried at room temperature for 1 day, and the contact angle with respect to dodecane was determined by DM700 manufactured by Kyowa Interface Science Co., Ltd. Measurement was performed using a fully automatic contact angle meter. The contact angle with water was measured by the expansion / contraction method.
The measurement results are shown in Table 2.

<Average particle size measurement>
About the transparent dispersion liquid of Example 4, the average particle diameter of the fine particle in it was measured by the dynamic light scattering method. As a result, the average particle diameter was about 225 nm, and the production of a fluorine-containing compound nanocomposite was confirmed.

  1 g of the nanocomposite transparent dispersion obtained in Example 4 was added to 1 g of urethane paint (RETAN PG80111BASE), 0.1 g of curing accelerator (RETAN PG80III HARDENER) was added, and then applied to a polypropylene plate at 105 ° C. And dried for 20 minutes. After 20 minutes, the mixture was allowed to cool to room temperature to obtain a coating film on which the nanocomposite had been applied.

  In Example 5, the same operation was performed except that the dispersion obtained by replacing the added amount of the silane coupling agent of Example 4 with isopropanol was used.

(Comparative Example 5)
In Example 5, 1 g of nanocomposite was replaced with 1 g of isopropanol, and the same operation was performed.

<Contact angle measurement>
The contact angles of water and dodecane on the surfaces of the dried coating films obtained in the above Examples and Comparative Examples were measured using a DM700 type fully automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Moreover, the dry coating film was peeled off from the polypropylene resin with a cello tape, and the contact angles of water and dodecane were similarly measured on the plate side (the back surface of the dry coating film).

  1 g of the nanocomposite transparent dispersion obtained in Example 4 was added to a mixed solution of 0.5 g of acrylic resin (S-744) and 0.5 g of distilled water, and then applied to a polypropylene plate and dried at 105 ° C. for 50 minutes. I let you. After 50 minutes, the mixture was allowed to cool to room temperature to obtain a resin coating to which the nanocomposite was applied.

  In Example 7, the same operation was performed except that the dispersion obtained by replacing the added amount of the silane coupling agent of Example 4 with isopropanol was used.

(Comparative Example 6)
In Example 7, 1 g of nanocomposite was replaced with 1 g of isopropanol, and the same operation was performed.

<Contact angle measurement>
The contact angle with respect to dodecane on the surface of the resin coating obtained in the above Examples and Comparative Examples was measured using a DM700 fully automatic contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Moreover, the resin film was peeled off from the polypropylene resin with a cello tape, and the contact angle of dodecane was similarly measured on the plate side (the back surface of the resin film). The contact angle with water was measured by the expansion / contraction method.

From the above, it can be seen that a desired nanomaterial or nanocomposite can be easily generated in the examples.
In addition, the dispersions of Examples 1 to 3 using the fluorine-containing compound according to the present invention have a contact angle with respect to dodecane that is much higher than that of Comparative Examples 1 to 3, excellent oil repellency, and water. It can be seen that the contact angle is high and the water repellency is also excellent.
Moreover, it turns out that hydrophilicity can be added in the dispersion liquid of Example 4 which uses the nanocomposite of the said fluorine-containing compound and a silane coupling agent. Furthermore, since the present silane coupling agent has a sulfo group, for example, by treating the coating surface with an aqueous solution containing sodium ions, ion exchange occurs and the hydrophilic performance can be further improved.
From these, the dispersion using the nanomaterial or nanocomposite of the present invention is subjected to surface treatment, thereby providing water / oil repellency to hard surfaces such as glass, metals, ceramics, plastics, painted plates of car bodies, etc. It can be seen that hydrophilicity and oil repellency can be imparted and a high antifouling effect is achieved.
On the other hand, in Examples 5 and 6, the surface of the dried coating film has a higher oil repellency effect than the back surface, and the effect is much higher than that of Comparative Example 5. Further, Example 5 shows hydrophilicity in water, and Example 6 shows water repellency. Therefore, it turns out that the nanomaterial or nanocomposite is efficiently oriented to the coating film surface side. Similarly, in Examples 7 and 8, the resin surface has a higher oil repellency effect than the back surface, and the effect is much higher than that of Comparative Example 6. Furthermore, Example 7 shows hydrophilicity in water and Example 8 shows water repellency. Therefore, more nanomaterials or nanocomposites are oriented in the surface side even in the resin.
From these, the dispersion using the nanomaterial or nanocomposite of the present invention can be added to paints, resins, etc., bone regeneration / restoration materials and dental materials, thereby providing water and oil repellency, hydrophilicity on the surfaces of these dry films. -It can be seen that oil repellency can be imparted and a high antifouling effect is achieved.

Claims (7)

Formula (I)
[Wherein Rf is a perfluoroalkyl group, a perfluorooxaalkyl group or a general formula
(In the formula, Af is a perfluoroalkylene group, Af ′ is the same or different perfluoroalkylene group as Af, and m is 1 to 10).
R is an alkyl group, an alkoxyalkyl group or a hydrogen atom, and n is 2 to 100. ]
And a fluorine-containing compound represented by the general formula (III)
[Wherein X is selected from the group consisting of vinyl group, styryl group, methacryloxy group, acryloxy group, amino group, quaternary ammonium group, ureido group, sulfide group, isocyanate group, alkoxy group, sulfo group and phosphate group. A is a divalent hydrocarbon group which may contain an oxygen atom, a nitrogen atom or a sulfur atom, R ¹ is a hydroxyl group, R ² is an alkyl group, an alkoxyalkyl group or hydrogen An atom and m is 1 or 2; ]
A nanocomposite comprising a silane coupling agent represented by: The fluorine-containing compound is represented by the formula (II)
[Wherein, R _F is represented by — (CF ₂ ) pF or —CF (CF ₃ ) O (CF ₂ CFCF ₃ O) qC ₃ F ₇ (p is 1 to 10, q is 0 to 5). Group, R 'is an alkyl group, n is 2-3. ]
The nanocomposite according to claim 1, which is represented by:   A nano-dispersed liquid in which the nanocomposite according to claim 1 or 2 is dispersed in a solvent.   The nano-dispersion according to claim 3, wherein the solvent is a non-aqueous solvent or a hydrophobic solvent.   The method for producing a nano-dispersion according to claim 3 or 4, wherein the fluorine-containing compound according to claim 1 or 2 and the silane coupling agent according to claim 1 are mixed in a solvent.   A coating agent comprising the nanodispersion according to claim 3 or 4.   An additive comprising the nanodispersion according to claim 3 or 4.