JP2010209280A - Fluorine-containing nanocomposite particle, and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide new fluorine-containing silica nanocomposite particles as a material utilizing the chemical and thermal stability of silica and the excellent water repellent, oil repellent, fouling-preventing and catalytic characters of a fluorine compound by using a fluorine low molecular surfactant as a raw material. <P>SOLUTION: The fluorine-containing silica nanocomposite particles includes a mixture of (A) silica nanoparticles and (B) a fluorine-containing surfactant expressed by formula (1) [wherein, T is SO<SB>3</SB>Q or COOQ; Q is H, Li, Na, K or the like; and Rf is 2C-8C fluoroalkyl] and a hydrolysate of a functional alkoxysilane, and/or a dehydrating condensate of the mixture. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to fluorine-containing silica nanocomposite particles and use thereof. Furthermore, the present invention relates to a surface treatment composition and a surface treatment method for treating the surface of a glass substrate, and more specifically, a surface treatment film containing novel silica nanocomposite particles is formed on the surface of a glass substrate, The present invention relates to a surface treatment composition and a surface treatment method capable of imparting antifouling property to a surface of a substrate in a general environment and high detergency in water such as a cleaning environment.

  2. Description of the Related Art Conventionally, a technique for imparting an antifouling function by performing a surface treatment using the water / oil repellency of a fluorine-containing oligomer is known (Patent Document 1). In addition, a technique has been conventionally known in which, by imparting a hydrophilic function to the surface of a fluorine-containing oligomer, even if dirt adheres to the surface, the dirt is easily removed by washing with water (Patent Document 2). On the other hand, regarding a photocatalyst such as titanium oxide, a base material on which a photocatalytic film having antifouling properties and hydrophilicity is formed is also known (Patent Document 3).

JP 2005-255720 A JP 2003-253250 A JP 2001-70801 A

  However, the fluorine-containing oligomer performs surface treatment having functions of oil repellency and water repellency (changes to hydrophilicity over time) on the surface of an inorganic material such as glass and imparts antifouling properties. Since the oligomer used as a raw material has a slightly complicated molecular structure and the use of a fluorine-based peroxide is essential, mass production is difficult.

  In addition, when using a photocatalyst film, although it has a function of easily removing dirt, generally, it is not particularly excellent in resistance to dirt. Therefore, in terms of antifouling, the function is superior. Sex was not recognized.

  In order to solve the above-mentioned problems, the present invention is a material that takes advantage of the chemical and thermal stability of silica and the excellent water repellency / oil repellency / antifouling / catalytic properties of a fluorine compound, and is easy at low cost. It is possible to provide a novel fluorine-containing silica nanocomposite particle using a low-molecular-weight fluorine-containing surfactant as a raw material, a surface treatment composition containing the fluorine-containing silica nanocomposite particle, It was made for the purpose of providing a surface treatment method with excellent antifouling property in general environment and high detergency in water by forming on the surface of the material, and excellent in heat resistance. is there.

The present invention relates to a fluorine-containing silica nanocomposite particle and a method for producing the same, and a surface treatment composition and a surface treatment method using the fluorine-containing silica nanocomposite particle.
(I) (A) silica nanoparticles,
(B) Formula (1):

Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. A fluorine-containing silica nanocomposite particle comprising a mixture of the indicated fluorine-containing surfactant and a hydrolyzate of a functional alkoxysilane and / or a dehydration condensate of the mixture.
(II) The (B) component functional alkoxysilane is represented by the formula (2):

(In the formula, R ₁ is hydrogen, a methyl group, an ethyl group, a hexyl group or a phenyl group, and R ₂ is a methyl group or an ethyl group. P and q are integers, and p + q = 4. The fluorine-containing silica nanocomposite particles according to the above (I), which is a compound represented by (.).
(III) The functional alkoxysilane (B) is at least one compound selected from the group consisting of tetramethoxysilane, tetraethoxysilane, trimethoxysilane, and triethoxysilane, (I) or ( II) Fluorine-containing silica nanocomposite particles.
(IV) The fluorine-containing silica nanocomposite particles according to any one of the above (I) to (III), wherein T in formula (1) is SO ₃ H or SO ₃ K, and R _f is linear.
(V) In thermogravimetric analysis, the rate of temperature increase is 10 ° C./min, and the weight loss when heated from room temperature to 800 ° C. is within ± 50% of the weight loss measured using silica particles. The fluorine-containing silica nanocomposite particles according to any one of (I) to (IV) above.
(VI) (A) silica nanoparticles,
(B1) Formula (1):

Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. A fluorine-containing surfactant shown,
(B2) After mixing the functional alkoxysilane,
A method for producing fluorine-containing silica nanocomposite particles, wherein the component (B1) and / or the component (B2) is hydrolyzed and / or dehydrated and condensed.
(VII) (A) silica nanoparticles;
(B1) Formula (1):

Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. A fluorine-containing surfactant shown,
(B2) a functional alkoxysilane;
(C) a solvent;
(D) A surface treatment composition containing an alkali catalyst or an acid catalyst.
(VIII) (B2) component is represented by formula (2):

(In the formula, R ₁ is hydrogen, a methyl group, an ethyl group, a hexyl group or a phenyl group, and R ₂ is a methyl group or an ethyl group. P and q are integers, and p + q = 4. The surface treatment composition according to (VII) above, which is a compound represented by.
(IX) The surface treatment composition according to (VII) or (VIII) above, wherein T in the formula (1) is SO ₃ H or SO ₃ K, and R _f is linear.
(X) Applying the surface treatment composition described in the above (VII) to (IX) to the surface of the glass substrate to form a coating film, heat-treating the coating film and the glass substrate, and surface A method for surface treatment of a glass substrate, comprising the steps of forming a treatment film in this order.

  According to the present invention (I), in a general environment (in the air), the water and oil repellency functions make it difficult to get dirt (high antifouling property), and in a cleaning environment (in water), oily dirt is removed due to hydrophilicity. Fluorine-containing silica nanocomposite particles having the contradictory properties of being easy to do (high detergency) are obtained. In addition, since the specific fluorine-containing surfactant that is a raw material has a relatively simple molecular structure, fluorine-containing silica nanocomposite particles can be produced easily and at low cost.

  According to the present invention (V), fluorine-containing silica nanocomposite particles having good thermal stability even at high temperatures can be obtained.

  According to the present invention (VI), since a specific fluorine-containing surfactant having a relatively simple molecular structure is used as a raw material, fluorine-containing silica nanocomposite particles can be produced easily and at low cost. Composite particles have excellent antifouling properties and high detergency.

  According to the present invention (VII), the fluorine-containing silica nanocomposite particles using a specific fluorine-containing surfactant having a relatively simple molecular structure as a raw material can be easily and at low cost, and can provide excellent protection on the surface of a glass substrate. A surface treatment composition capable of imparting dirtiness and high detergency is obtained.

  According to the present invention (X), the surface treatment composition can impart excellent antifouling properties and high detergency to the glass surface easily and at low cost.

1 is a reaction scheme 1 relating to Examples 1 and 2. FIG. It is a figure which shows the result of the thermogravimetric analysis of the fluorine-containing silica nanocomposite particle obtained in Examples 5 and 6. It is a figure which shows the result of the thermogravimetric analysis of the silica nanoparticle used for the raw material. It is a figure which shows the result of the thermogravimetric analysis of the fluorine-containing silica nanocomposite particle obtained in Examples 7-11. It is a figure which shows the result of the ¹⁹ F NMR measurement in the heavy methanol solution of the fluorine-containing silica nanocomposite particle obtained in Example 7. HO ₃ shows the results of _{S (CF 2) 3 SO 3} H 19 F NMR measurements. It is a figure which shows the result of the thermogravimetric analysis of the fluorine-containing silica nanocomposite particle obtained in Examples 12-16. It is a figure which shows the result of the ¹⁹ F NMR measurement in the heavy methanol solution of the fluorine-containing silica nanocomposite particle obtained in Example 12. HO ₃ shows the results of _{S (CF 2) 3 SO 3} H 19 F NMR measurements.

  Hereinafter, the present invention will be specifically described based on embodiments. Unless otherwise indicated,% is based on mass unless otherwise specified.

[Fluorine-containing silica nanocomposite particles]
The fluorine-containing silica nanocomposite particles of the present invention include (A) silica nanoparticles,
(B) Formula (1):

Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. It comprises a mixture of the indicated fluorine-containing surfactant and a hydrolyzate of functional alkoxysilane and / or a dehydration condensate of the mixture.

  As the component (A), the average particle size is preferably 5 to 200 nm, and more preferably 10 to 100 nm. Here, the average particle diameter is measured by a dynamic light scattering method. In addition, examples of the shape of the component (A) include a spherical shape and an elliptical shape, but a spherical shape is preferable.

  (A) A component may be used individually or in combination of 2 or more types.

  The fluorine-containing surfactant as the component (B) has the formula (1):

Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. As shown, both ends of the fluoroalkyl group (Rf) are sulfonic acid or sulfonate, or one end is sulfonic acid or sulfonate and the other end is carboxylic acid or carboxylate. The fluoroalkyl group does not need to be linear and may be branched. The carbon number of the fluoroalkyl group is selected from the viewpoint of the yield in the electrolytic fluorination step and the solubility in a solvent or the like used in the subsequent step, and this carbon number is preferably 2 to 5. R _f is preferably linear.

  As the fluorine-containing surfactant as the component (B), the formula (1a):

(Wherein, Q and Rf are as defined in formula (1)), and from the viewpoint of acid strength, HO ₃ S (CF ₂ ) ₃ SO ₃ H, KO ₃ S (CF ₂ ) ₃ SO ₃ K is more preferable. HO ₃ S (CF ₂ ) ₃ COOH is also preferable.

    The fluorine-containing surfactant as component (B) can be synthesized by a method known to those skilled in the art by electrolytic fluorination.

  The component (B) fluorine-containing surfactant may be used alone or in combination of two or more.

  The functional alkoxysilane of component (B) is preferably a polyfunctional alkoxysilane, and has the formula (2):

Wherein R ₁ is hydrogen, methyl group, ethyl group, hexyl group or phenyl group, R ₂ is methyl group or ethyl group, p is 3 or 4, and p and q are integers And p + q = 4) is more preferable. In formula (2), when p is 3, q is 1, R ₁ is a methyl group, an ethyl group or a hexyl group, or when p is 4, q is more preferably 0.

Here, in the formula (2), when p is 3, it becomes a trialkoxysilane represented by the formula [R ₁ Si (OR ₂ ) ₃ ], for example, triethoxysilane, triethoxy (methyl) silane, triethoxy (phenyl) Examples include silane, trimethoxysilane, trimethoxy (methyl) silane, and trimethoxy (phenyl) silane. When p is 4, q is 0 and becomes a tetraalkoxysilane of the formula [Si (OR ₂ ) ₄ ], and examples thereof include tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS). Of these, tetraalkoxysilane is even more preferable, and TMOS and TEOS are particularly preferable because they are liquid and highly compatible with specific fluorine-containing surfactants. The contained silica nanocomposite particles can be made homogeneous.

  As the functional alkoxysilane of the component (B), two or more kinds of the above-mentioned various polyfunctional alkoxysilanes can be mixed and used. For example, when some trialkoxysilane is added to tetraalkoxysilane, or when a part of tetraalkoxysilane is replaced with trialkoxysilane, the compatibility between the fluoroalkyl group-containing surfactant and the functional alkoxysilane increases. Thus, the crosslinkability in the fluorine-containing silica nanocomposite particle structure is improved, and the curability and durability of the coating film of the surface treatment composition using this are improved. Further, the same effect can be obtained by adding colloidal silica or sodium silicate, substitution with polyfunctional alkoxysilane, and addition of calcium / phosphorus compound.

  The component (B) is a mixture of the fluorine-containing surfactant and a functional alkoxysilane hydrolyzate and / or a dehydration condensate of the mixture. Here, this hydrolyzate is a product obtained by hydrolyzing a functional alkoxysilane by a method known to those skilled in the art, and the dehydration condensate is a fluorine-containing surfactant and / or the hydrolyzate. A product obtained by dehydration condensation by heat treatment or the like. The hydrolyzate may contain unreacted functional alkoxysilane.

  The fluorine-containing silica nanocomposite particles of the present invention preferably contain 2 to 90 parts by mass of component (A) with respect to 100 parts by mass in total of components (A) and (B) from the viewpoint of production. 70 parts by mass is more preferable.

  Moreover, it is preferable that 2-90 mass parts of fluorine-type surfactant of (B) component is included with respect to a total of 100 mass parts of (A) and (B) component, and 5-70 mass parts is more preferable. When the content ratio of the fluorine-based surfactant as the component (B) is less than 2 parts by mass, it is difficult to impart functions such as antifouling properties and high detergency. On the other hand, even if it contains the fluorine-type surfactant of (B) component in the ratio exceeding 90 mass parts, the process effect corresponding to content is not acquired.

  It is preferable from a manufacturing viewpoint to contain the hydrolyzate of the functional alkoxysilane of (B) component with respect to a total of 100 mass parts of (A) and (B) component. 20-80 mass parts is more preferable.

  The mass ratio of the component (B) fluorine-containing surfactant and the functional alkoxysilane is preferably 1: 1 to 1:20, more preferably 1: 1 to 1:10. When the content ratio of the functional alkoxysilane with respect to the fluorine-containing surfactant of the component (B) is less than the above, the compatibility between the fluorine-containing surfactant and the functional alkoxysilane deteriorates and phase separation occurs. The possibility that the fluorine-containing silica nanocomposite particles become cloudy is increased, and it may be difficult to form uniform fluorine-containing silica nanocomposite particles. On the other hand, if this ratio is excessive, the ratio of the fluorine low-molecular surfactant becomes relatively small, and it may be difficult to impart the desired effect to the fluorine-containing silica nanocomposite particles.

  The fluorine-containing silica nanocomposite particles of the present invention may contain various optional components in addition to the essential components as long as the effect is not impaired.

  In the thermogravimetric analysis, the fluorine-containing silica nanocomposite particles of the present invention have a temperature increase rate of 10 ° C./min in an air atmosphere, and the weight loss when heated from room temperature to 800 ° C. is 0 to 8% by mass, It is preferable that the thermal stability is good even at a high temperature when it is almost the same as the raw material silica nanoparticles, that is, within ± 50% of the weight loss when measured using the silica nanoparticles. This weight loss is often observed in the range of -20 to 50%. In addition, the water | moisture content adsorb | sucked to this silica nanoparticle etc. can be considered as a cause by which a weight reduction | decrease is less than the case of a fluorine-containing silica nanocomposite particle | grain from measuring this silica nanoparticle. Since the fluorine-containing silica nanocomposite particles of the present invention contain a fluorine compound having a sulfonic acid group, the possibility as a solid electrolyte material such as Nafion is also considered. That is, due to thermal stability at high temperatures, the fluorine-containing silica nanocomposite particles of the present invention are expected to be applied as materials for solid electrolytes such as fuel cells.

  The method for producing fluorine-containing silica nanocomposite particles of the present invention comprises (A) silica nanoparticles and (B1) formula (1):

Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. A fluorine-containing surfactant shown,
(B2) After mixing the functional alkoxysilane,
The component (B1) and / or (B2) is hydrolyzed and / or dehydrated and condensed.

  The component (A) is as described above.

  About (B1) component, it is as the fluorine-containing surfactant described in the said (B) component, About (B2) component, it is as the functional alkoxysilane described in the said (B) component.

  Specifically, the fluorine-containing silica nanocomposite particles are prepared by adding an (A) component, a (B1) component, and a (B2) component to a solvent, and then stirring the solvent while using an alkali catalyst or an acid catalyst. An aqueous solution containing a functional alkoxysilane is added to the hydrolyzate, and if necessary, this solvent is heated to a part or all of the mixture of the fluorine-containing surfactant and the functional alkoxysilane hydrolyzate by a heating step or the like. Can be easily produced by making a dehydration condensate. The solvent, alkali catalyst, and acid catalyst will be described later.

  The heating method in the heating step for dehydration condensation is not particularly limited, such as heating with an oven. Examples of the heating conditions include normal temperature to 200 ° C. for 5 to 120 minutes, and preferable conditions include normal temperature to 100 ° C. for 5 to 60 minutes.

  The mixture of the fluorine-containing surfactant and the functional alkoxysilane hydrolyzate is subjected to heat treatment, whereby the fluorine-containing surfactant and / or the functional alkoxysilane hydrolyzate undergoes dehydration condensation, Fluorine-containing silica nanocomposite particles are formed. Here, the reaction is insufficient to proceed at room temperature or lower, and at 200 ° C. or higher, the decomposition reaction of the substance before hydrolysis and / or before dehydration condensation occurs by heat treatment, and the fluorine-containing silica nanocomposite particles as a reaction product It becomes difficult to form. In addition, after this heat treatment, stability at high temperature is imparted to the fluorine-containing silica nanocomposite particles.

[Surface treatment composition]
The surface treatment composition of the present invention comprises (A) silica nanoparticles,
(B1) Formula (1):

Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. A fluorine-containing surfactant shown,
(B2) a functional alkoxysilane;
(C) a solvent;
(D) An alkali catalyst or an acid catalyst is contained.

  The component (A) is as described above.

  About (B1) component, it is as the fluorine-containing surfactant described in the said (B) component, About (B2) component, it is as the functional alkoxysilane described in the said (B) component.

  The component (C) can be selected from liquids that can dissolve both the component (B1) and the component (B2), and methanol varies depending on the types of the component (B1) and the component (B2). , Ethanol, IPA, tetrahydrofuran, chloroform, benzene, ethyl acetate, dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF), toluene, acetone and the like, and among these, methanol and Alcohols such as ethanol are preferred.

  (C) A component may be used individually or in combination of 2 or more types.

  The component (D) is added in order to efficiently perform hydrolysis and / or dehydration condensation of the component (B1) and the component (B2). Here, the hydrolysis is considered to occur mainly by the component (B2). Dehydration condensation mainly depends on the hydrolyzate of component (B2), but it is considered that it can also occur between the hydrolyzate of component (B2) and component (B1), and can also occur between components (B1). .

  Examples of the alkali catalyst of component (D) include ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium hydrogen carbonate and the like. It is preferable to use both an alkali catalyst and an inorganic acid catalyst in an aqueous solution from the viewpoint of causing a reaction such as hydrolysis homogeneously. In this case, in the case of an alkali catalyst, it is preferable that it is 10-90 mass parts with respect to 100 mass parts of (D) component. Component (D) is preferably an alkali catalyst, and ammonium water is particularly preferable because it easily volatilizes during the heating step. In addition, when the hydrolysis of (B2) occurs during storage due to the addition of the component (D) and the viscosity of the surface treatment composition becomes excessively high, it is preferable to store the surface treatment composition at a low temperature.

  (D) A component may be used individually or in combination of 2 or more types.

  10-80 mass parts of (A) component is included with respect to a total of 100 mass parts of (A), (B1), (B2), (C), and (D) component of the surface treatment composition of this invention. From the viewpoint of physical properties such as thermal stability at high temperatures.

  (B1) component contains 0.2-20 mass parts with respect to a total of 100 mass parts of (A), (B1), (B2), (C) and (D) of the surface treatment composition of this invention. Is preferable, and 0.5-10 mass parts is more preferable. When the content ratio of the component (B1) is less than 0.2 parts by mass, it is difficult to impart functions such as antifouling properties and high detergency. On the other hand, even if the content rate of (B1) component exceeds 20 mass parts, the process effect corresponding to content is not acquired.

  The component (B2) contains 2 to 50 parts by mass with respect to 100 parts by mass in total of the components (A), (B1), (B2), (C) and (D) of the surface treatment composition of the present invention. From the viewpoint of production, 5 to 30 parts by mass is more preferable.

  The mass ratio of the component (B1) to the component (B2) is preferably 1: 1 to 1:20, more preferably 1: 1 to 1:10. When the content ratio of the (B2) component to the (B1) component is less than the above, the compatibility between the (B1) component and the (B2) component deteriorates, phase separation occurs, or fluorine-containing silica nanocomposite particles May become cloudy and it may be difficult to form uniform fluorine-containing silica nanocomposite particles. On the other hand, when this ratio is excessive, the ratio of the fluorine low molecular surfactant is relatively small, and it may be difficult to impart the desired effect to the glass surface.

  5 to 90 parts by mass of the component (C) is included with respect to 100 parts by mass in total of the components (A), (B1), (B2), (C) and (D) of the surface treatment composition of the present invention. From the viewpoint of production, it is preferable.

  When the component (D) is an alkali catalyst, the component (D) is based on 100 parts by mass of the total of the components (A), (B1), (B2), (C) and (D) of the surface treatment composition. It is preferable to contain 0.01-30 mass parts, and 1-20 mass parts is more preferable. When the amount is less than 0.01 parts by mass, the effect as a catalyst cannot be obtained. When the amount is more than 30 parts by mass, the compatibility of the components (B1) and (B2) is significantly deteriorated, and a uniform surface treatment composition is obtained. Becomes difficult.

  In addition, the surface treatment composition of this invention may contain various arbitrary components other than said essential component in the limit which the effect is not impaired.

  The surface treatment composition of the present invention can be easily manufactured by adding the components (A) and (D) after dissolving the components (B1) and (B2) in the component (C). it can. Here, if an example of a manufacturing method is shown, the solution which dissolve | melts (B1) component in a suitable quantity of (C) component, and (B2) component will stir and mix at room temperature, and will be made homogeneous, There can be mentioned a method in which the component (A) and the component (D) are added to prepare a mixed solution, and then the remaining component (C) is added to dilute the mixed solution.

  The surface treatment composition of the present invention can be used for the surface treatment of a glass substrate. On the surface of the glass substrate, antifouling (water and oil repellency) and high detergency (hydrophilic) conflicts. It is possible to give the characteristics to be.

[Glass substrate surface treatment method]
The treatment method of the present invention comprises a step of applying the surface treatment composition of the present invention on the surface of a glass substrate to form a coating film, and heat-treating the coating film with the surface treatment composition to form a surface treatment film. The steps of forming are included in this order. In the coating process, as a method for applying the surface treatment composition to the surface of the glass substrate, a coating method such as a dipping method in which the glass substrate is immersed in the surface treatment composition, a spray, a brush, a roller, or the like is used. A method using a printing method is not particularly limited. In addition, after completion | finish of this application | coating process, in order to remove a solvent from the coating film formed in the surface of an inorganic material, it is preferable to perform a drying process. As drying conditions, although it changes also with the kind of solvent which comprises a process composition, and a content rate etc., 1 to 24 hours are mentioned at normal temperature, for example.

  The component (B2) in the surface treatment composition is generally hydrolyzed during application and / or drying. Water necessary for hydrolysis is supplied from water contained in component (D), moisture in the air, or the like. If hydrolysis does not occur sufficiently during the coating and drying, hydrolysis continues until the next heating step.

  The heating method in the heating step after forming the coating film is not particularly limited, such as heating with an oven. Examples of the heating conditions include normal temperature to 200 ° C. for 5 to 120 minutes, and preferable conditions include normal temperature to 100 ° C. for 5 to 60 minutes.

  Surface treatment containing fluorine-containing silica nanocomposite particles by hydrolyzing and / or dehydrating and condensing component (B1) and / or (B2) by subjecting the coating applied to the surface of the glass substrate to heat treatment A layer is formed. Here, the reaction is insufficient to proceed at room temperature or lower, and at 200 ° C. or higher, the decomposition reaction of the substance before hydrolysis and / or before dehydration condensation occurs by heat treatment, and the fluorine-containing silica nanocomposite particles as a reaction product It becomes difficult to form. In addition, after this heat treatment, stability at high temperature is imparted to the fluorine-containing silica nanocomposite particles.

  In addition, this surface treatment composition has a durability of the surface treatment film by performing hydrolysis and / or dehydration condensation reaction under an alkali catalyst, compared with the case where the reaction is carried out under an acid catalyst. Can be improved. As a result, antifouling properties (water and oil repellency) and high resistance imparted by the surface treatment film against chemical and physical effects associated with cleaning operations such as dishwashers using water or hot water The detergency (hydrophilicity) is not significantly impaired. Thus, the said surface treatment film | membrane obtained by reacting under an alkali catalyst has the outstanding washing | cleaning durability compared with what was obtained by reacting under an acid catalyst. Furthermore, the improvement in productivity accompanying the improvement of the transparency of the surface treatment film and the shortening of the reaction time is recognized as an effect.

  The surface treatment layer formed by the surface treatment composition of the present invention has excellent water and oil repellency due to the action of a fluoroalkyl group (fluorine) exposed on the surface in a general environment (in the air). Demonstrates antifouling properties. When washing (in water), sulfonic acid groups come out on the surface instead of fluorine and become hydrophilic, and the oil comes out from the surface when water enters between the oil stain and the surface treatment layer. It will have sex.

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

Examples 1 and 2
As a fluorine-containing surfactant, 0.2 g of HO ₃ S (CF ₂ ) ₃ SO ₃ H was dissolved in about 30 ml of methanol, 3.33 g of methanol silica sol (30% nanosilica, average particle size: 11 nm), and 0.3 wt. 5 ml was added, and finally 0.5 ml of 28% aqueous ammonia was added with stirring to react for 5 hours. Subsequently, in order to remove ammonia water, the solvent was removed by an evaporator, 10 ml of methanol was added, and the mixture was stirred and dispersed overnight. Furthermore, it wash | cleaned several times with methanol with the centrifuge, 10 ml of methanol was added again, and it stirred overnight and disperse | distributed. Thereafter, the particle size was measured by the dynamic light scattering method.

  FIG. 1 shows reaction scheme 1. Table 1 shows the types of fluorine-containing surfactants and the yield of fluorine-containing silica nanocomposite particles when prepared according to Reaction Scheme 1 and the average particle diameter by dynamic light scattering (dynamic light scattering photometer manufactured by Otsuka Electronics Co., Ltd.) Model number: DLS-7000HL)).

  As shown in Table 1, in both Examples 1 and 2, fluorine-containing silica nanocomposite particles having an average particle diameter of about 94 and 54 nm were obtained.

[Examples 3 and 4]
0.5 g of silica nanoparticles, 0.30 g of a fluorine-containing surfactant represented by XO ₃ S (CF ₂ ) ₃ SO ₃ X, 0.25 ml of Si (OC ₂ H ₅ ) ₄ and 10 ml of methanol Then, 0.5 ml of 28% by mass ammonia water was mixed using a magnetic stirrer to prepare a surface treatment composition.

  The prepared surface treatment composition was cast on both sides of a polymethyl methacrylate (PMMA) film to prepare a coating film. This coating film was treated under vacuum at room temperature for 12 days to produce a surface-treated film. Here, the back surface is the back surface of the PPMA film.

[Evaluation of surface treatment film 1]
25 μl of dodecane (hereinafter referred to as oil) is dropped on the obtained surface treatment film, and the angle (unit: degree) formed at the contact portion between the glass substrate and the oil droplet is determined as the contact angle of G-1-1000 manufactured by ERMA. Measurement was performed with a measuring instrument. It can be said that the higher the contact angle value, the easier the oil is repelled in the air, that is, the higher the antifouling property. (Hereinafter, the angle formed between the glass substrate and the oil droplets is called the oil-in-water contact angle (degrees) or simply the oil-in-water angle (degrees).)

[Evaluation 2 of surface treatment film]
The oil was dropped on the obtained surface treatment film, the glass substrate was further immersed in water, and the contact angle between the glass substrate and the oil droplet was measured with the contact angle measuring device. It can be said that the higher the contact angle value, the easier the oil can be removed in water, that is, the higher the cleaning angle. This contact angle measurement was performed at intervals of 5 minutes until 30 minutes passed after being immersed in water.

  Table 2 shows the results of the evaluations 1 and 2 described above (the aerial oil droplet contact angle is “oil”, and the oil-in-water measurement result is “water”). It is understood that the glass substrate subjected to the surface treatment of the present invention has high antifouling properties and high cleaning properties, particularly in the initial state.

[Examples 5 and 6]
Fluorine-containing silica nanocomposite particles were produced in the same manner as in Example 1 except that the composition shown in Table 3 was used.

  Table 4 shows the yield and yield of the obtained fluorine-containing silica nanocomposite particles and the average particle diameter measured by the dynamic light scattering method.

  As shown in Table 4, in both Examples 5 and 6, fluorine-containing silica nanocomposite particles having an average particle size of about 60 and 56 nm were obtained.

Thermogravimetric analysis of the obtained fluorine-containing silica nanocomposite particles was carried out from room temperature using a high-temperature differential scanning calorimeter (model number: AXS2000SA) manufactured by Bruker AXS, at a heating rate of 10 ° C./min. Measured up to 800 ° C. FIG. 2 shows the result. For reference, FIG. 3 shows the results of thermogravimetric analysis of the silica nanoparticles used as the raw material. The weight reduction of the fluorine-containing silica nanocomposite particles of Example 6 was 110% or less, that is, + 10% or less of the weight reduction of the silica particles used as the raw material. Table 5 shows the average particle diameter measured by the dynamic light scattering method before and after the weight loss and temperature increase. Table 5 also shows the theoretical content (% by mass) of KO ₃ S (CF ₂ ) ₃ SO ₃ K.

As shown in Table 5, in both Examples 5 and 6, the weight loss was as small as 7 and 5% by mass, suggesting that KO ₃ S (CF ₂ ) ₃ SO ₃ K remained. Further, the average particle size before and after the temperature increase was almost the same.

[Examples 7 to 11]
Fluorine-containing silica nanocomposite particles were produced in the same manner as in Example 1 except that the composition shown in Table 6 was used.

  Table 7 shows the yield and yield of the obtained fluorine-containing silica nanocomposite particles and the average particle diameter measured by the dynamic light scattering method.

  As shown in Table 7, in all of Examples 7 to 11, fluorine-containing silica nanocomposite particles having an average particle size of about 36 to 45 nm were obtained.

Thermogravimetric analysis of the obtained fluorine-containing silica nanocomposite particles was measured in the same manner as in Example 5. The result is shown in FIG. Table 8 shows the average particle diameter measured by the dynamic light scattering method before and after the weight loss and temperature increase. Table 8 also shows the theoretical content (% by mass) of HO ₃ S (CF ₂ ) ₃ SO ₃ H.

As shown in Table 8, in all of Examples 7 to 11, the weight loss is as small as 7 to 9% by mass, suggesting that HO ₃ S (CF ₂ ) ₃ SO ₃ H remains. Further, the average particle size before and after the temperature increase was almost the same.

Next, ¹⁹ F NMR measurement in a deuterated methanol solution of the fluorine-containing silica nanocomposite particles obtained in Example 7 was performed using a JEOL FT NMR apparatus (model number: JNM-400). The result is shown in FIG. For comparison, FIG. 6 shows the results of ¹⁹ F NMR measurement of HO ₃ S (CF ₂ ) ₃ SO ₃ H. Two peaks of CF ₂ groups (-114 ppm, −120 ppm) indicating that the fluorine-containing silica nanocomposite particles contain HO ₃ S (CF ₂ ) ₃ SO ₃ H were confirmed.

[Examples 12 to 16]
Fluorine-containing silica nanocomposite particles were produced in the same manner as in Example 1 except that the composition shown in Table 9 was used.

  Table 10 shows the yield and yield of the obtained fluorine-containing silica nanocomposite particles and the average particle diameter measured by the dynamic light scattering method.

  As shown in Table 10, in all of Examples 12 to 16, fluorine-containing silica nanocomposite particles having an average particle size of about 30 to 87 nm were obtained.

Thermogravimetric analysis of the obtained fluorine-containing silica nanocomposite particles was measured in the same manner as in Example 5. The result is shown in FIG. Table 11 shows the average particle diameter measured by the dynamic light scattering method before and after the weight loss and temperature increase. Table 11 also shows the theoretical content (mass%) of HO ₃ S (CF ₂ ) ₃ COOH.

As shown in Table 11, in all of Examples 12 to 16, the weight loss was as small as 6 to 8% by mass, suggesting that KO ₃ S (CF ₂ ) ₃ COOH remained. Further, the average particle size before and after the temperature increase was almost the same.

The zeta potential of the fluorine-containing silica nanocomposite particles obtained in Example 12 before and after the temperature increase in the thermogravimetric analysis was measured by using a zeta potential measuring device (model number: Zeecom / ZC-2000) manufactured by Microtech / Nichion. . Table 12 shows the results. For comparison, the average particle diameter and zeta potential measured by the dynamic light scattering method of SiO ₂ used as a raw material are shown.

As shown in Table 12, in Example 12, the zeta potential lower than that of SiO ₂ was exhibited even after the temperature increase.

Next, the result of ¹⁹ F NMR measurement in a deuterated methanol solution of the fluorine-containing silica nanocomposite particles obtained in Example 12 is shown in FIG. For comparison, FIG. 9 shows the result of ¹⁹ F NMR measurement of HO ₃ S (CF ₂ ) ₃ COOH. Three peaks of CF ₂ groups (−114 ppm, −119 ppm, −122 ppm) indicating that the fluorine-containing silica nanocomposite particles contain HO ₃ S (CF ₂ ) ₃ COOH were confirmed.

  As shown in the above examples, the fluorine-containing silica nanocomposite particles of the present invention are ultrafine and stable even at high temperatures, and the glass substrate subjected to the surface treatment of the present invention has high antifouling properties and high cleaning performance. It was found to have sex.

Claims (10)

(A) silica nanoparticles;
(B) Formula (1):
Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. A fluorine-containing silica nanocomposite particle comprising a mixture of the indicated fluorine-containing surfactant and a hydrolyzate of a functional alkoxysilane and / or a dehydration condensate of the mixture. The functional alkoxysilane of component (B) is represented by formula (2):
(In the formula, R ₁ is hydrogen, a methyl group, an ethyl group, a hexyl group or a phenyl group, and R ₂ is a methyl group or an ethyl group. P and q are integers, and p + q = 4. The fluorine-containing silica nanocomposite particles according to claim 1, which is a compound represented by.   The fluorine-containing compound according to claim 1 or 2, wherein the functional alkoxysilane of component (B) is at least one compound selected from the group consisting of tetramethoxysilane, tetraethoxysilane, trimethoxysilane, and triethoxysilane. Silica nanocomposite particles. A T is SO ₃ H or SO ₃ K of the formula (1), _{R f} is a straight chain, a fluorine-containing silica nanocomposite particle of any one of claims 1 to 3.   In thermogravimetric analysis, the weight loss when heated from room temperature to 800 ° C. at a heating rate of 10 ° C./min is within ± 50% of the weight loss measured using silica nanoparticles. The fluorine-containing silica nanocomposite particles according to any one of -4. (A) silica nanoparticles;
(B1) Formula (1):
Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. A fluorine-containing surfactant shown,
(B2) After mixing the functional alkoxysilane,
A method for producing fluorine-containing silica nanocomposite particles, wherein the component (B1) and / or the component (B2) is hydrolyzed and / or dehydrated and condensed. (A) silica nanoparticles;
(B1) Formula (1):
Wherein T is SO ₃ Q or COOQ, Q is hydrogen, lithium, sodium, potassium, rubidium or cesium, and Rf is a fluoroalkyl group having 2 to 8 carbon atoms. A fluorine-containing surfactant shown,
(B2) a functional alkoxysilane;
(C) a solvent;
(D) A surface treatment composition containing an alkali catalyst or an acid catalyst. The component (B2) is represented by the formula (2):
(Wherein R ₁ is hydrogen, a methyl group, an ethyl group, a hexyl group or a phenyl group, R ₂ is a methyl group or an ethyl group. P is 3 or 4. p and q are integers. And p + q = 4.) The surface treatment composition according to claim 7. The surface treatment composition according to claim 7 or 8, wherein T in the formula (1) is SO ₃ H or SO ₃ K, and R _f is linear.   The surface treatment composition according to any one of claims 7 to 9 is applied to the surface of a glass substrate to form a coating film, and the coating film and the glass substrate are heat-treated, and the surface treatment is performed. A method for treating a surface of a glass substrate, comprising the steps of forming a film in this order.