JP2013060354A - Fingerprint resistant film forming processing agent and fingerprint resistant glass having the film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing agent for forming a fingerprint resistant film in which stains such as fingerprints sticking to the surface is not visible, which is excellent in both fingerprint resistance and adhesiveness between the film and the surface of a substrate, a processing agent for forming the fingerprint resistant film excellent in the abrasive resistance of the film, a processing agent for forming a fingerprint resistant film improving finger slidability, and a fingerprint resistant glass substrate having the film comprising those processing agents.SOLUTION: The fingerprint resistant film forming processing agent is characterized in that a compound A in which hydroxyl groups of a monool or a polyol containing at least one structure selected from a group consisting an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain as a repeating unit are modified by a silicon compound is the film forming component. The fingerprint resistant glass is characterized by having the fingerprint resistant film formed by the processing agent. Further, the fingerprint resistant glass substrate is characterized in that the finger slidability is enhanced by providing unevenness to the surface of the substrate by a fine powder such as colloidal silica.

Description

  The present invention relates to a fingerprint-resistant film-forming treatment agent for making it difficult to visually recognize a fingerprint attached through a film formed on the surface of a glass substrate, and a fingerprint-resistant glass having the film.

  Glass substrates are widely used as displays for electronic devices, automobile parts, buildings, and the like. Depending on the part of use, these base materials have many opportunities to be touched by human hands, so that dirt derived from living organisms such as fingerprints and sebum (hereinafter simply referred to as “fingerprint component”) can easily adhere to them. There was a property that could not be wiped off. In particular, the glass substrate is characterized by transparency, but the fingerprint component adhering to the glass substrate and / or the fingerprint component that has not been completely wiped off are very noticeable. In recent years, touch panels have been widely used as input methods for electronic devices such as personal computers, mobile phones, medical devices, car navigation systems, and automated teller machines (ATMs), and this type of display surface can be touched by a finger. However, the above problems due to the fingerprint component have become apparent.

In order to solve the above problems, surface treatment of the base material and reduction of the surface energy of the base material make it difficult for the fingerprint component to adhere to the base material and make it difficult to become familiar with the base material. Attempts have been made to increase the resistance to fingerprint components. For example, in Patent Document 1, a layer of a silicon-containing organic fluorine-containing polymer represented by the following general formula (I) and having a number average molecular weight of 5 × 10 ² to 1 × 10 ⁵ is formed on the surface of a substrate. A characteristic antifouling substrate is described.

  However, it is difficult to completely prevent the fingerprint component from adhering to the substrate. In recent years, as another approach to the above problem, the adhesion of the fingerprint component to the substrate is less noticeable, or the fingerprint component can be easily adapted to the substrate. It is an issue. In Patent Document 2, by forming a lipophilic film on the surface of the base material, the fingerprint component attached through the film formed on the surface of the base material wets and spreads. Patent Document 3 discloses a photocurable hydrophilic coating agent that forms a hydrophilic film having high fingerprint wiping properties and high surface hardness on the surface of a substrate.

  On the other hand, in glass used for touch panel operation such as touching with a human finger, for improved operability, there is little catching between the finger and the substrate surface when the finger touches the substrate surface. It is required to have slipperiness (hereinafter referred to as “finger slipperiness”). Regarding the improvement of finger slipperiness, a method of imparting surface roughness to the contact surface between the finger and the substrate is known. For example, Patent Document 4 discloses a polyolefin-based resin film with improved finger slipperiness. No. 5 discloses a glass for a touch panel imparted with an antiglare function and finger slipperiness by giving a specific surface roughness.

JP 09-157582 A JP 2001-353808 A International Publication No. 2011-013497 JP 2004-35757 A JP 2005-38288 A

  In the case of the lipophilic molecule of Patent Document 2 and the hydrophilic film of Patent Document 3, it is difficult to say that the fingerprint resistance is sufficient. Further, in the case of a resin film such as Patent Document 3, the adhesion between the resin and the glass substrate is weak, There was a problem that peeling of the film occurred.

  Therefore, the present invention forms a film having good lipophilicity on the glass substrate surface and a film having good adhesion to the glass substrate surface as a method for making it difficult to visually recognize the attached fingerprint. Providing a treatment agent is a first problem.

  In addition, fingerprint-resistant glass is often used for applications that can be touched by a human finger, such as a touch panel cover glass, and is often wiped with a cloth during cleaning, so the abrasion resistance of the film is also important. Therefore, the present invention provides a treatment agent for obtaining a coating film having good fingerprint resistance, good adhesion between the film and the glass substrate, and good film abrasion resistance. Let it be the second issue.

  Furthermore, this invention makes it a 3rd subject to obtain a glass base material with favorable fingerprint resistance and finger-slip property using the said processing agent.

  The present invention provides an anti-fingerprint film-forming treatment agent (hereinafter sometimes simply referred to as “treatment agent”) for forming a surface layer capable of imparting fingerprint resistance to a glass substrate. The treating agent is a compound A in which the hydroxyl group of a monool or polyol containing at least one structure selected from the group consisting of an ethylene oxide chain, a propylene oxide chain and a butylene oxide chain as a repeating unit is modified with a silicon compound (hereinafter referred to as a compound A). , Which may be simply described as “Compound A”) as a film-forming component.

The present invention also provides a fingerprint-resistant film-forming treatment agent, wherein the compound A is a compound having a structure represented by any one of the general formulas [1] to [4]. is there.

(In the formula, R represents a polymerization site containing at least one chain structure selected from the group consisting of an ethylene oxide chain, a propylene oxide chain and a butylene oxide chain as a repeating unit, and X represents —C (═O) —N ( —H) — group or —CH ₂ —CH ₂ — group, R ′ represents an alkylene group having 1 to 3 carbon atoms, Y is independent from each other, an alkoxy group having 1 to 4 carbon atoms, chloro And at least one hydrolyzable functional group selected from the group consisting of a group and an isocyanate group, a is an integer of 0 to 1, p and q are integers of 0 to 3, and Z is independent. And represents a hydrogen atom, a —R—OH group, or a substituent represented by the following formula, and at least one of Z in the molecule is a substituent of the following formula.

(In the formula, R, X, R ′, Y, and a are the same as in the general formula [1].)

  Furthermore, the present invention provides a fingerprint-resistant film-forming treatment agent characterized in that at least a polycondensate of the compound A and a silicon oxide precursor is used as a film-forming component.

  Furthermore, the present invention provides a fingerprint-resistant film-forming treatment agent, wherein the treatment agent further contains inorganic oxide fine particles.

  Furthermore, this invention provides the anti-fingerprint film formed with the said processing agent.

  Furthermore, the present invention provides a fingerprint-resistant glass having a film formed by the treatment agent.

  Furthermore, the present invention has a base film having a concavo-convex structure containing inorganic oxide fine particles on the surface of a glass substrate, and has a fingerprint resistance film formed on the surface of the base film by the treatment agent. Glass is provided.

  Furthermore, the present invention provides the fingerprint-resistant glass, wherein the inorganic oxide fine particles are colloidal silica having an average particle size of 10 to 500 nm.

  Furthermore, the present invention provides the fingerprint-resistant glass, wherein the arithmetic average surface roughness of the coating surface is 2 to 300 nm.

  Further, the present invention is characterized in that after the base film containing inorganic oxide fine particles is formed on the surface of the glass substrate to provide a concavo-convex structure, a film is formed on the surface of the base film with the treatment agent. A method for producing fingerprint glass is provided.

  In the present invention, “fingerprint resistance” means the difficulty of visually recognizing the fingerprint component adhering to the substrate surface. An evaluation method of “fingerprint resistance” will be described in Examples described later. In the present invention, the “fingerprint resistance” can be said to be more effective as the “lipophilicity” of the substrate surface is better. Therefore, lipophilicity is evaluated as one index for measuring fingerprint resistance. The evaluation method of “lipophilicity” is also described in the examples.

  In the present invention, “silicon oxide” may include not only stoichiometric silicon dioxide but also low-order silicon oxide.

  According to the present invention, it is possible to obtain a fingerprint-resistant glass substrate having a fingerprint-resistant coating film having good fingerprint resistance and good adhesion between the coating film and the glass substrate surface. Moreover, according to this invention, the glass substrate which has a fingerprint-resistant film with favorable fingerprint resistance, the adhesiveness of a film | membrane and a glass base material, and abrasion resistance can be obtained. Furthermore, it is possible to obtain a fingerprint-resistant glass substrate having a fingerprint-resistant coating film with good finger slipperiness.

Schematic cross-sectional schematic diagram showing an example of the fingerprint-resistant transparent substrate of the present invention Schematic cross-sectional schematic diagram showing an example of the fingerprint-resistant transparent substrate of the present invention Schematic cross-sectional schematic diagram showing an example of the fingerprint-resistant transparent substrate of the present invention Schematic cross-sectional schematic diagram showing an example of the fingerprint-resistant transparent substrate of the present invention The optical photograph instead of drawing showing a mode that the pseudo fingerprint was made to adhere to the base material obtained in Example 2 of this invention. An optical photograph in place of a drawing showing a pseudo-fingerprint attached to a general float glass substrate that has not been surface-treated. The figure which shows the evaluation result of abrasion resistance.

  The present invention provides a film-forming compound A in which the hydroxyl group of a monool or polyol containing a repeating unit containing at least one chain structure selected from the group consisting of an ethylene oxide chain, a propylene oxide chain and a butylene oxide chain is modified with a silicon compound An anti-fingerprint film-forming treatment agent characterized by comprising a component. By forming a film on a glass substrate using this treatment agent, fingerprint resistance can be suitably imparted to a glass substrate.

  The compound A particularly has a structure in which the hydroxyl group of a monool or polyol containing at least one chain structure selected from the group consisting of an ethylene oxide chain, a propylene oxide chain and a butylene oxide chain as a repeating unit is modified with a silicon compound. It is not limited. Examples of the compound A include structures such as the general formulas [1] to [4].

  In the general formulas [1] to [4], R represents a polymerization site containing at least one chain structure selected from the group consisting of an ethylene oxide chain, a propylene oxide chain, and a butylene oxide chain as a repeating unit. A copolymer structure of at least two different chains in the group is preferable. This polymerization site may be formed only by a chain selected from the above group, or a hydrocarbon group, a nitrogen atom, an oxygen atom, or the like may exist between the chains. It is presumed that when this polymerization site forms a layer on the glass substrate surface, the lipophilicity of the substrate surface is improved and good fingerprint resistance can be imparted.

In the formula, X represents a —C (═O) —N (—H) — group or a —CH ₂ —CH ₂ — group. Y represents at least one hydrolyzable functional group selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a chloro group, and an isocyanate group. When the functional group causes a hydrolysis reaction, a chemical bond is formed between the glass substrate and the silanol group, and the adhesion between the base material and the coating film is improved.

  In the formula [1], if the reactivity of the hydrolyzable functional group represented by Y is too high, not only is the handling difficult when preparing the treating agent, but the pot life of the treating agent is shortened. On the other hand, if the reactivity is too low, the hydrolysis reaction will not proceed sufficiently, and the amount of silanol groups produced will not be sufficient, so the bonds formed between the silanol groups and the active species on the substrate surface ( For example, siloxane bonds and other metalloxane bonds) and interactions (for example, van der Waals forces and electrostatic interactions) are not sufficient, and sufficient adhesion between the coating and the substrate surface is achieved. It cannot be applied, or the durability of the coating is lowered. In view of the above, the hydrolyzable functional group represented by Y is selected from the group consisting of alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, chloro group, and isocyanate group. At least one selected is preferred. Among these, considering the ease of handling the hydrolyzable functional group, the pot life of the treatment agent, and the durability of the resulting coating, the hydrolyzable functional group is preferably an alkoxy group, among which a methoxy group, An ethoxy group is particularly preferred.

The compound A can be easily synthesized from a monool or polyol containing at least one chain structure selected from the group consisting of an ethylene oxide chain, a propylene oxide chain and a butylene oxide chain as a repeating unit and a silicon compound. is there. For example, by using polyethylene glycol as the polyol and 3-isocyanatopropyltrimethoxysilane as the silicon compound and reacting in the presence of a catalyst, the target product can be obtained as shown in the following scheme.

  Examples of monools or polyols that can be used for synthesis include polyoxypropylene glycol monoalkyl ether monool type, polyethylene glycol, polypropylene glycol diol type, polypropylene glycol triol type, poly (oxyethylene / polyoxypropylene) Examples include glycol monoalkyl ether, polyoxyethylene polyoxypropylene glycol, polyoxypropylene glycol monoalkyl ether, glyceryl stearate, and polybutylene glycol. Examples of silicon compounds that can react with the hydroxyl groups of these polyols include 3-isocyanatopropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

  Examples of the catalyst used for the synthesis include dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin marker butylate, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin marker butylide, Dioctyl tin thiocarboxylate and the like can be used. The catalyst concentration to be added may be in the range of 0.1 to 10% by mass with respect to the isocyanate compound.

  As the compound A contained in the anti-fingerprint coating agent, only one type of compound having the structure as described above may be used, or a plurality of types of compounds may be used in combination.

  By using the anti-fingerprint coating agent containing Compound A as a film-forming component, it is possible to form a film with good fingerprint resistance and good adhesion between the film and the substrate surface on the glass substrate surface. . One form of the glass base material which has a film formed with the processing agent which consists of a compound A is shown in FIG.

  The treatment agent is preferably diluted with an organic solvent as a coating solution. When the treatment agent is diluted with a solvent, the concentration of the compound A may be about 0.01 to 50% by mass. The organic solvent to be used is not particularly limited as long as it dissolves the compound A and does not deactivate it. Specifically, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, normal propyl alcohol, butanol, acetone, and methyl ethyl ketone are used. , Ketones such as methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate. Of these, isopropyl alcohol and methyl ethyl ketone are preferred.

  As the treating agent, a polycondensate of compound A and a precursor of silicon oxide (hereinafter also simply referred to as “polycondensate”) may be used as a film forming component. When the treating agent contains a polycondensate of compound A and a silicon oxide precursor, the silicon oxide precursor may be used in an amount of about 0.01 to 100 moles per mole of the compound A. The precursor of silicon oxide is not only stoichiometric silicon dioxide, but also low-order silicon oxide, a part of oxygen chemically bonded to lipophilic molecules and matrix, and the network in amorphous materials such as glass. It means what includes silicon oxide as a forming oxide (specific compounds will be described later). The film formed from the polycondensate is presumed to contribute to the improvement of wear resistance. Therefore, it can be said that the treatment agent contains a polycondensate of compound A and a silicon oxide precursor. FIG. 2 shows an embodiment of a glass substrate having a coating formed by a treating agent comprising a polycondensate of compound A and a silicon oxide precursor.

  Examples of the precursor of silicon oxide include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, Butyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, and alkyltrialkoxysilanes whose methoxy groups are ethoxy, propoxy, isopropoxy, etc., 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyl Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl triethoxysilane, 3-oxetanyl-triethoxysilane and the like can be used. These may be used alone or in combination. Considering the wear resistance of the coating and the cost of the chemical, among these, preferred are tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, 3-glycol. Sidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane.

  Further, an acid catalyst may be added to the treatment agent. Although there is no restriction | limiting in particular as an acid catalyst, Hydrochloric acid, nitric acid, a sulfuric acid, an acetic acid etc. are mentioned. The amount of compound A may be about 0.001 to 100 moles per mole of compound A.

  Further, when the treatment agent contains a polycondensate of compound A and a silicon oxide precursor, a predetermined amount of inorganic oxide fine particles (hereinafter sometimes simply referred to as “fine particles”) is further added to the treatment agent. You can also. The fine particles generally mean particles having an average particle size of 1 μm or less. By including fine particles in the treatment agent, it is possible to impart a concavo-convex structure to the surface of the film to be formed, and the concavo-convex structure can reduce the contact area between the finger and the surface of the film, thereby improving finger slipping. It can be said that this is one of the preferred forms. One form of the glass substrate which has the film formed with the said processing agent is shown in FIG.

  Specific examples of the inorganic oxide fine particles added to the treatment agent include particles such as silica, alumina, titania, zirconia, tin oxide, indium-containing tin oxide, antimony-containing tin oxide, zinc oxide, and hollow silica. Particles and tin oxide particles are preferred. Although there is no restriction | limiting in particular in the particle shape of this inorganic oxide microparticles | fine-particles, Usually, they are spherical shape, ellipse shape, rectangular shape, and polyhedral shape. Specific examples of the inorganic oxide fine particles include colloidal silica, colloidal alumina, colloidal titania, and colloidal tin oxide. Among them, the use of colloidal silica is preferable because good bondability with a glass substrate can be obtained. When the average particle size of the inorganic oxide fine particles is 10 to 500 nm, it is easy to impart appropriate roughness to the surface. An average particle size of 10 to 200 nm is preferable because the formed film has good hardness, and 10 to 100 nm is particularly preferable. When the particle size is smaller than 10 nm, it is difficult to provide a sufficient uneven structure on the film surface.

  The “average particle diameter” in the present invention refers to an average particle diameter obtained by assuming that the particles are spheres from the surface area measured by the BET method. The BET method is one of the methods for measuring the surface area of a powder by a vapor phase adsorption method, and is a method for obtaining the total surface area, that is, the specific surface area of a 1 g sample from an adsorption isotherm. Usually, nitrogen gas is used as the adsorbed gas, and a method of measuring the amount of adsorption from the change in pressure or volume of the gas to be adsorbed is common. A prominent expression of the isotherm of multimolecular adsorption is the Brunauer Emmett and Teller equation (BET equation). Based on this, the amount of adsorption is obtained, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface. . From the surface area obtained, assuming that the particles are spheres, the average particle size, ie the particle size referred to in the present invention, is obtained.

  Moreover, it is preferable that 5-95 mass% of inorganic oxide microparticles | fine-particles are contained with respect to the total mass of the film formation component of a processing agent, More preferably, it is 20-80 mass%. When the content of the fine particles is less than 5% by mass, a sufficient uneven structure cannot be imparted to the film surface. Conversely, when the content is more than 95% by mass, a large amount of fine particle aggregates are observed, and uneven coating occurs during coating. It may occur and is not preferable.

  Further, with respect to the inorganic oxide fine particles, the wear resistance can be improved by mixing fine particles having different average particle diameters at an appropriate ratio.

  Further, instead of adding inorganic oxide fine particles to the treatment agent, a film containing a predetermined amount of inorganic oxide fine particles is formed on the surface of the glass substrate to give an uneven structure, and then the compound A is further applied to the surface of the film. It is also a preferred form to form a fingerprint-resistant film with a treating agent as a film forming component. The inorganic oxide fine particles may be the same as or different from the inorganic oxide fine particles added to the treatment agent. Among these, use of colloidal silica is preferable because good bonding with a glass substrate can be obtained.

  In this case, two layers of a film having a concavo-convex structure (hereinafter sometimes simply referred to as “undercoat film”) and a fingerprint-resistant film formed on the surface of the undercoat film are formed on the glass substrate. It becomes a film structure. One form is shown in FIG. Since the film 2 formed of the treatment agent composed of the compound A is thin, it does not impair the concavo-convex structure of the base film 5 including the fine particles 4, and effectively has fingerprint resistance and finger resistance on the surface of the two-layer film. The slipperiness can be expressed.

  The base film is not particularly limited, but is preferably a film having a concavo-convex structure containing fine particles in a film obtained by hydrolysis and polycondensation of a silicon oxide precursor from the viewpoint of wear resistance. As the silicon oxide precursor, the same compounds as those used in the treatment agent described above can be used.

  Next, the glass substrate will be described. Although there is no restriction | limiting in particular in the glass base material of this invention, Specifically, the glass etc. which consist of soda-lime silicate glass, aluminosilicate glass, quartz glass, an alkali free glass, other various glass etc. are mentioned, for example. Further, these glass substrates can be used as clear glass, colored glass, template glass, antiglare glass, UV, IR cut glass and other functional glass, tempered glass, semi-tempered glass, laminated glass and other safety glass. . In addition to these inorganic glasses, plastic glass species such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate and the like which can be used as organic glasses can also be used.

  The shape of the substrate is appropriately determined depending on the application. Preferably they are a sheet form and a film form.

  In addition, an appropriate haze can be imparted to the substrate by imparting an appropriate surface roughness. If the initial haze is high, the attached fingerprint is less noticeable. Further, depending on the shape of the uneven structure, antiglare property and finger slipping property can be imparted. In the case of imparting antiglare properties, the surface roughness can be appropriately changed depending on the use of the substrate, but it is usually preferable that the arithmetic average roughness Ra is 120 to 500 nm. More preferably, it is 120-400 nm. The arithmetic average roughness referred to here is defined in JIS B0601 (2001), and can be measured using a stylus type surface scanner or the like. However, increasing the haze or anti-glare property may lead to a reduction in the sharpness of the image seen through the glass substrate. 3 and FIG. 4 are adopted, and it is preferable to adjust the average particle size and content of the fine particles used so that the surface roughness according to the application is obtained. When emphasizing the visibility, the preferable surface roughness is 2 to 100 nm, and particularly preferably 2 to 50 nm.

  Next, a method for forming a fingerprint-resistant film on a glass substrate using the treatment agent of the present invention will be described. In the case of a treating agent having Compound A as a film-forming component, the treating agent can be diluted with a solvent and used as a coating solution, and a coating film can be formed after the coating solution is applied to the substrate surface. Any coating method may be used as long as it is a generally known method, such as a dip coating method, a spray method, a spin coating method, a flow coating method, a vapor deposition method, and a brush coating method. , Roll coating method, squeegee method and the like. Among them, preferred are spray method, spin coating method, flow coating method, vapor deposition method, brush coating method, and squeegee method. Particularly preferred are the spin coating method, flow coating method and squeegee method. In the case of the vapor deposition method, the treatment agent may be used as it is without being diluted with a solvent.

  When apply | coating the processing agent of this invention to a base material with a spin coating method, a coating liquid is dripped on the rotating base material, and a liquid is spread and apply | coated to the whole base material with a centrifugal force.

  Moreover, when applying a flow coating method, the nozzle flow coating method and the curtain flow coating method are mentioned. When applying to the substrate by the nozzle flow coating method, the coating solution is supplied from a single or a plurality of nozzles, and the coating solution is applied to the substrate conveyed horizontally or the rotating disk-shaped substrate. A flattened film can be obtained on the material. Also, when applying to the substrate by curtain flow coating, the coating liquid flows down in a curtain shape from the storage tank for storing the processing liquid as the coating liquid to the substrate via the coating liquid supply path. A coating film flattened on the base material can be obtained by supplying the coating liquid to the head part for the purpose and passing the base material in the horizontal direction below the head part.

  In addition, when applying to a substrate by the squeegee method, a member such as cloth, sponge, brush, brush, non-woven fabric is held by a means such as impregnating and infiltrating the coating solution, and the member is attached to the robot or human hands. The coating solution is applied onto the substrate by bringing it into contact with the substrate. Or after supplying a coating liquid to a base material, members, such as cloth, sponge, a brush, a brush, and a nonwoven fabric, may be contacted with the coating liquid, and the supplied coating liquid may be extended. Further, a combination of these may be used.

  After applying the coating solution, the coating can be formed by standing at room temperature or heating. The heating temperature is not particularly limited because it depends on the structure of Compound A, but it is usually preferably 50 to 250 ° C, more preferably 100 to 200 ° C.

  When using a polycondensate of compound A and a silicon oxide precursor as a film-forming component as the treating agent, it is particularly advantageous to form a fingerprint-resistant film by a sol-gel method. This is advantageous from the point of view. The film formation by the sol-gel method may be in accordance with a regular method. At the time of preparation of a sol obtained by hydrolyzing and / or polycondensing a silicon oxide precursor, the compound A is mixed and dispersed in the silicon oxide precursor, and the obtained sol is used as the coating solution to form a glass. By forming a film on the base material, a film made of a polycondensate of compound A and a silicon oxide precursor is formed.

  Even when the treatment agent further contains fine particles, it is particularly preferable to form a film by a sol-gel method from the viewpoint of film formability and wear resistance. At the time of preparation of the sol described above, the compound A and fine particles are mixed and dispersed in a silicon oxide precursor, and the resulting sol is used as the coating liquid to form a film on a glass substrate. A film made of a condensation polymer of the precursor of silicon and silicon oxide and fine particles is formed.

  Further, when forming a two-layer film of a base film and an anti-fingerprint film, the base film is first formed on the surface of the substrate to give a concavo-convex structure, and then Compound A is used as a film-forming component by the method described above. A fingerprint-resistant film may be formed on the surface of the base film with the treating agent. The undercoat film is preferably formed on the surface of the glass substrate by using a sol-gel method. A sol solution containing the inorganic oxide fine particles and the silicon oxide precursor is prepared and formed on the substrate. A basement film is formed. The amount of fine particles contained in the sol solution is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, based on the total mass of the film-forming components (inorganic oxide-based fine particles and silicon oxide precursor). is there.

  In the preparation of the sol obtained by hydrolysis and / or polycondensation of the above-mentioned silicon oxide precursor, the solvent contained in the sol is not limited as long as the sol can be uniformly applied to the substrate surface. An organic solvent that can dissolve and disperse the solid content in the sol appropriately is preferable because it can be easily handled. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and butyl acetate, aliphatic hydrocarbons such as hexane, decane and cyclohexane, toluene, Aromatic hydrocarbons such as xylene and mixtures thereof are preferred. Moreover, a mixed solution of two or more of these solvents may be used. Furthermore, the solid content concentration of the sol may be a concentration of about 0.01 to 50% by mass. In addition, when preparing sol using the commercial item as said microparticles | fine-particles, the solvent contained in this commercial item can be used as it is as a part of solvent of the sol prepared by this invention.

  In addition, a catalyst for promoting hydrolysis and polycondensation reaction may be added to the sol used in the present invention as described above. The catalyst to be used is not particularly limited, and examples thereof include hydrochloric acid, nitric acid, sulfuric acid, acetic acid and the like. The amount of addition is preferably a normal amount of catalyst, and may be about 0.001 to 100 mol per mol of the solid content in the sol.

  In addition, it is preferable to add a surfactant to the sol used in the present invention as described above in order to adjust the dispersibility of the fine particles within a range not impairing the object of the present invention. As the surfactant, general anionic and nonionic surfactants can be used. For example, fluorine-based surfactants and polyether-modified organosiloxanes can be considered.

  Moreover, the application | coating method similar to the processing agent which uses the compound A mentioned above as a film formation component can be used for the coating method to the glass base material of sol for forming a base film. After applying the sol, the base film having a concavo-convex structure is formed by allowing it to stand at room temperature or heating. It is preferable to perform heating temperature at 50-700 degreeC normally, More preferably, it is 100-500 degreeC.

  In the fingerprint-resistant film of the present invention, how the compound A molecule or the polycondensate of the compound A and the silicon oxide precursor is dispersed is determined as long as there is no significant bias in the lipophilicity of the substrate surface. Regardless of whether it is uniformly dispersed or concentrated on the film surface, it may be concentrated on the interface between the film and the substrate, but it is preferably in a uniformly dispersed state.

  The thickness of the anti-fingerprint film of the present invention is not particularly limited, but is usually about 1 to 1000 nm. In the case of a film made of Compound A, the film thickness depends on the molecular structure of the compound used, but is usually about 1 to 1000 nm. In the case of a film containing silicon oxide, the thickness of the coating is not particularly limited, but is preferably 200 nm or less. In the case of 200 nm or less, since the wavelength is sufficiently smaller than the wavelength of visible light, film formation unevenness is not conspicuous, and the film strength depends on the glass substrate and becomes hard. Further, when the coating film is a two-layer coating film, the fingerprint-resistant coating film formed on the surface of the base film has a thickness of about 1 to 1000 nm, which is preferable without impairing the irregularities on the surface of the base film.

  It is preferable that the glass substrate on which the fingerprint-resistant film is formed by the treatment agent of the present invention can have a static contact angle of 10 ° or less when 2 μl of oleic acid at room temperature is placed on the surface of the substrate. When the contact angle is 10 ° or less, the surface has very high lipophilicity, and the attached fingerprint component can be spread and become inconspicuous visually.

In addition, the glass substrate on which the fingerprint-resistant film is formed by the treatment agent of the present invention, the surface of the substrate is horizontally oriented under a condition in which a load is applied perpendicularly to the surface at about 30 g / cm ² using a towel. In terms of wear resistance, the static contact angle when 2 μl of oleic acid is placed on the surface of the substrate at room temperature after 300 reciprocating wipes has a change rate within 50% of the contact angle before wiping. It is preferable from the viewpoint.

  Details will be described below, but the present invention is not limited to these examples.

[Evaluation of lipophilicity]
As an evaluation of the lipophilicity of the obtained substrate, about 2 μl of oleic acid was placed on the surface of the substrate, and the angle formed by the droplet and the substrate surface 10 seconds after the droplet was placed was measured using a contact angle meter (CA− Measurement was performed at room temperature (about 25 ° C.) using X200, manufactured by Kyowa Interface Science.

[Evaluation of wear resistance]
As the evaluation of the abrasion resistance of the obtained base material, the evaluation of lipophilicity after reciprocating while sliding on the surface of the base material with a strength of about 30 g / cm ^{2 with} a general towel 120 mm was used. The contact angle was measured by the above method every 50, 100, 200, and 300 reciprocations.

[Evaluation of hardness]
As an evaluation of the hardness of the obtained base material, a pencil hardness test was performed using Uni (6B-9H) manufactured by Mitsubishi Pencil Co., Ltd. according to “JIS K 5600-5-4 (1999)”.

[Fingerprint resistance evaluation method]
The following (1) to (2) were performed as evaluation of fingerprint resistance of the obtained substrate.

(1) Pseudo-fingerprint adhesion test End surface of a silicone rubber plug with a diameter of 29 mm is used as an artificial finger roughened with a base material Cw, abrasive material A, and abrasive paper of particle size P240 specified in JIS R6252, on an acrylic substrate Quantitative pseudo-fingerprint adhesion test was conducted using oleic acid spin-coated with a thickness of 0.5 mm as an artificial fingerprint liquid. By artificially pressing an artificial finger against an acrylic substrate at 250 g / cm ² , the artificial fingerprint liquid is transferred to the artificial finger, and similarly at 250 g / cm ² against the substrate to be evaluated, the substrate is pressed vertically. A pseudo-fingerprint was attached to the surface.

(2) Evaluation of fingerprint resistance The fingerprint resistance was visually evaluated when a pseudo fingerprint was attached. (○ not noticeable, △ not noticeable, but visible at a specific angle, equivalent to × raw substrate)
[Evaluation of finger slipping: sensory evaluation]
The surface of the substrate was reciprocated 10 times with a finger, and the finger slipping property was evaluated. (Better than the evaluation of the substrate of Comparative Example 1. ΔEquivalent to the substrate of Comparative Example 1, × Worse than the substrate of Comparative Example 1)
[Evaluation of finger slipping: Evaluation of dynamic friction coefficient]
The dynamic friction coefficient of the substrate was measured using a static friction measuring machine (Handy Tribomaster Type TL201Ts manufactured by Trinity Labs). A tactile contact having a pattern imitating a fingerprint of a finger is used as the contact, and the frictional force between the substrate and the contact is measured under the conditions of a load of 20 g, a friction speed of 20 mm / sec, and a friction distance of 50 mm. The dynamic friction coefficient was obtained by the analysis software.

[Evaluation of surface roughness]
Based on JIS-B0601 (2001), the arithmetic average roughness of the obtained base material was evaluated. Using a scanning probe microscope (SPM-9600, manufactured by Shimadzu Corporation), the surface shape of 10 μm square was analyzed, and the arithmetic average roughness (Ra) was determined by a general-purpose program attached to the apparatus.

(Method for Synthesizing Compound A)
A synthesis procedure and a mixing ratio (mass ratio) are shown. First, propylene glycol; 2.00 g and methyl ethyl ketone (dehydrated product); 17.76 g were mixed and stirred for about 1 minute, and then dibutyltin dilaurate; 0.03 g was added and stirred for about 5 minutes. Further, 3-isocyanatopropyltrimethoxysilane was added so that the isocyanate group (—N═C═O) and the OH group of propylene glycol were 1: 1 equivalent, and the mixture was stirred at room temperature for 1 day. The FT-IR spectrum of the obtained solution was measured, about 2300 cm -N = C = peak intensity derived from the O group is reduced appearing near ^-1, generating a peak derived from N-H in the vicinity of 1530 cm ^-1 Therefore, silanized polypropylene glycol having three alkoxy groups at the terminal is generated by the reaction of the OH group of polypropylene glycol and the —N═C═O group of 3-isocyanatopropyltrimethoxysilane. it is conceivable that.

[Example 1]
A typical float glass substrate having a size of 100 mm square and a thickness of 2 mm was cleaned, and the compound A synthesized by the above synthesis method was diluted to 1% by mass with methyl ethyl ketone as a coating solution and applied by hand. . Bencot (manufactured by Asahi Kasei Fibers Co., Ltd.) was used as a member for hand painting. After coating, the substrate was held for 10 minutes in an electric furnace maintained at 150 ° C. to obtain a base material in which the treatment agent was bonded to glass.

As shown in Table 1, the contact angle of oleic acid was 8 ^° , indicating good lipophilicity. Furthermore, the fingerprint trace when the pseudo-fingerprint was attached was not noticeable visually. Further, as shown in FIG. 7, the contact angle of oleic acid was 16 ^° after sliding back and forth 300 times with a towel.

[Example 2]
In Example 1, the same conditions as in Example 1 were used except that the float glass as the base material was a general anti-glare glass (Ra = 140 nm) and the surface having the uneven structure of the base material was surface-treated. As shown in Table 1, the contact angle of oleic acid was 7 ^° , indicating good lipophilicity. Further, the fingerprint trace when the pseudo fingerprint was attached was not noticeable visually. Furthermore, as shown in FIG. 7, the contact angle of oleic acid after sliding back and forth 300 times with a towel was 16 ^° .

[Example 3]
In order to use a polycondensate of compound A and a precursor of silicon oxide as a film-forming treatment agent, 100 ml of commercially available tetraethoxysilane is used as a precursor of silicon oxide, 250 ml of isopropyl alcohol and 50 ml of 1N nitric acid are used. The added solution is stirred at room temperature for 12 hours, 50 g of compound A synthesized by the above method and 500 ml of methyl ethyl ketone are mixed, and the solution is stirred at room temperature for 2 hours, so that polycondensation of compound A and tetraethoxysilane is achieved. Got the body. The conditions were the same as in Example 1 except that the obtained product was used as it was as a coating solution. As shown in Table 1, the contact angle of oleic acid was 8 ^° , indicating good lipophilicity. Further, the fingerprint trace when the pseudo fingerprint was attached was not noticeable visually. Furthermore, as shown in FIG. 7, the contact angle of oleic acid after sliding back and forth 300 times with a towel was 8 ^° , indicating good wear resistance.

[Example 4]
In Example 3, the same conditions as in Example 3 were applied except that the float glass as the base material was general anti-glare glass (Ra = 140 nm), and the surface having the uneven structure of the base material was surface-treated. As shown in Table 1, the contact angle of oleic acid was 7 ^° , indicating good lipophilicity. Further, the fingerprint trace when the pseudo fingerprint was attached was not noticeable visually. Furthermore, as shown in FIG. 7, the contact angle of oleic acid after sliding back and forth 300 times with a towel was 8 ^° , indicating good wear resistance.

[Comparative Examples 1-2]
A typical float glass substrate or antiglare glass having a size of 100 mm square and a thickness of 2 mm was cleaned to obtain a target glass substrate.

  Next, an example of a fingerprint-resistant glass having a base film having a concavo-convex structure containing inorganic oxide fine particles on the surface of the glass substrate and having a coating formed on the surface of the base film with a processing agent is described. To do.

(Method for preparing sol solution)
After 5.33 g of isopropyl alcohol and 1.2 g of 1N nitric acid were added to 3.47 g of commercially available tetraethoxysilane and the solution was stirred at room temperature for 16 hours, 40 g of isopropyl alcohol was further added, and the solid content concentration was 2% by mass. A silica sol solution was obtained. Moreover, 1 part by mass of colloidal silica (MEK-ST, manufactured by Nissan Chemical Industries, Ltd., particle size 10 to 15 nm) and 14 parts by mass of methyl ethyl ketone were mixed to obtain a colloidal silica solution having a solid content concentration of 2 mass percent. These were mixed so that the colloidal silica content shown in Table 2 (the content here is mass% with respect to the total mass of the film-forming component) was obtained to obtain a sol solution for forming a base film.

[Examples 5 to 8]
A general float glass substrate having a size of 100 mm square and a thickness of 2 mm was cleaned, and the sol solution prepared by the above-described method was applied. After the application, the glass substrate was held in an electric furnace maintained at 150 ° C. for 10 minutes to obtain a glass substrate on which a base film having a concavo-convex structure was formed. The film thickness of the obtained base film was about 100 nm.

  Next, the same processing agent as in Example 1 was applied to the surface of the obtained glass substrate by hand coating and heated at 150 ° C. for 10 minutes, whereby the glass having a concavo-convex structure and a fingerprint-resistant coating on the surface. A substrate was obtained.

[Examples 9 to 12]
In the above sol solution preparation method, a sol solution prepared under the same conditions was used except that MEK-ST-2040 (particle size: 200 nm) manufactured by Nissan Chemical Industries, Ltd. was used as colloidal silica. After obtaining a glass substrate on which a base film having an uneven structure was formed on the surface in the same manner as in Examples 5 to 8, the same treatment agent as in Example 1 was applied by hand and heated at 150 ° C. for 10 minutes. As a result, a glass substrate having a concavo-convex structure and a fingerprint-resistant coating on the surface was obtained. Table 2 shows the conditions of the fine particles used in each case and the evaluation results of the obtained base material.

[Reference Example 1]
A general float glass substrate having a size of 100 mm square and a thickness of 2 mm was cleaned, and the sol solution used in Example 5 was applied. After the application, the glass substrate was held in an electric furnace maintained at 150 ° C. for 10 minutes to obtain a glass substrate on which a film having a concavo-convex structure was formed.

  The fingerprint-resistant substrate of the present invention exhibits excellent fingerprint resistance in an environment where a finger or the like is easily touched and a fingerprint component is easily attached. Specifically, architectural window glass and showcases (for store products, dolls, etc.), partitioning substrates, electrical and electronic equipment (TVs, mobile phones, PCs, ATMs, photo plates, etc.) displays By using it for a panel, a touch panel, an electronic device casing, a mirror, a beverage bottle, a beverage glass, etc., an excellent antifouling effect can be imparted such that fingerprints and the like are hardly noticeable.

DESCRIPTION OF SYMBOLS 1 Base material 2 Anti-fingerprint film 3 Anti-fingerprint film 4 by processing agent containing polycondensate of compound A and silicon oxide precursor Inorganic oxide fine particle 5 Base film

Claims (10)

  A treatment agent for forming a film on a glass substrate, wherein the hydroxyl group of a monool or polyol containing at least one structure selected from the group consisting of an ethylene oxide chain, a propylene oxide chain and a butylene oxide chain as a repeating unit is silicon. An anti-fingerprint film-forming agent comprising a compound A modified with a compound as a film-forming component. The treatment agent according to claim 1, wherein the compound A according to claim 1 is a compound having a structure represented by any one of the general formulas [1] to [4].
(In the formula, R represents a polymerization site containing at least one chain structure selected from the group consisting of an ethylene oxide chain, a propylene oxide chain and a butylene oxide chain as a repeating unit, and X represents —C (═O) —N ( —H) — group or —CH ₂ —CH ₂ — group, R ′ represents an alkylene group having 1 to 3 carbon atoms, Y is independent from each other, an alkoxy group having 1 to 4 carbon atoms, chloro And at least one hydrolyzable functional group selected from the group consisting of a group and an isocyanate group, a is an integer of 0 to 1, p and q are integers of 0 to 3, and Z is independent. And represents a hydrogen atom, a —R—OH group, or a substituent represented by the following formula, and at least one of Z in the molecule is a substituent of the following formula.
(In the formula, R, X, R ′, Y, and a are the same as those in the general formula [1].)   An anti-fingerprint film-forming agent comprising a polycondensate of the compound A according to claim 1 or 2 and a silicon oxide precursor as a film-forming component.   The anti-fingerprint film-forming agent according to claim 3, wherein the anti-fingerprint film-forming agent comprises inorganic oxide fine particles.   A fingerprint-resistant film formed by the anti-fingerprint film-forming agent according to any one of claims 1 to 4.   An anti-fingerprint glass having a film formed by the anti-fingerprint film forming agent according to any one of claims 1 to 4.   A coating film formed on the surface of the glass substrate with a base film having a concavo-convex structure containing inorganic oxide fine particles and formed on the surface of the base film with the treatment agent according to any one of claims 1 to 3. Has anti-fingerprint glass.   The fingerprint-resistant glass according to claim 7, wherein the inorganic oxide fine particles according to claim 7 are colloidal silica having an average particle size of 10 to 500 nm.   9. The fingerprint-resistant glass according to claim 6, wherein an arithmetic average surface roughness of the coating surface is 2 to 300 nm.   After forming the base film containing inorganic oxide fine particles on the surface of the glass substrate and imparting a concavo-convex structure, a film is formed on the surface of the base film with the treatment agent according to any one of claims 1 to 3. The method for producing fingerprint-resistant glass according to any one of claims 6 to 8, characterized in that it is characterized in that: