JPH0827456A - Surface traeting agent and base subjected to surface treatment - Google Patents

Abstract

PURPOSE:To obtain a surface treating agent useful for providing a base having excellent stain resistance, water repellency, chemical resistance, wear resistance and weather resistance, capable of treating the surface of a base at normal temperature, containing a specific silicone compound. CONSTITUTION:This surface treating agent contains (A) a silicone compound of formula I [R<1> to R<6> are each H or an organic group (with the proviso that one or more of R<1> to R<6> are organic groups); Z<1> to Z<3> are each kn isocyanate group or a hydrolyzable group; (a) to (f) are each 0-2; a+b is 1-3; c+d is 0-2; e+f is 1-3; a+b+c+d+e+f is 2-7; (n) is >=0] or formula II (R<1>f and R<2>f are each a polyfluoro organic group) and further (B) a compound of formula III (R<7> to R<9> are each H or a 1-30C organic group; (p), (q) and (r) are each 0-3; p+q+r is 0-3). The surface of a base is preferably treated with the surface treating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel surface treatment agent for room temperature treatment and a substrate treated with the surface treatment agent.
More specifically, it relates to a surface treatment agent capable of imparting excellent water repellency and antifouling property to the surface of a substrate such as glass, plastics, ceramics and metal, and a substrate treated with the surface treatment agent.

[0002]

2. Description of the Related Art Base materials made of various materials and various base materials having a surface treatment layer applied to the base materials are used in all fields, but adsorption of dust, oil stains, etc. to the surface of the base material,
Alternatively, the adverse effect of water has become a problem.

For example, the outer plates, window glass, mirrors, outer layer members such as surface materials for display devices, inner layer members such as surface materials for instrument panels, and the surface of other articles in transportation equipment such as trains, automobiles, ships, and aircraft are always Although it is preferably clean, there is a problem in that the appearance is impaired when raindrops, dust, dirt, and the like adhere to the surface, or when water condenses due to the influence of humidity and temperature in the atmosphere. Further, if the surface is in direct contact with human eyes or is in direct contact with human eyes, discomfort and hygiene problems occur.

Further, the dirt on the article for transportation equipment may significantly deteriorate the original function. In particular, articles for transportation equipment are required to be transparent and transparent (for example,
In the case of a window glass, a mirror, etc.), the decrease in transparency and see-through means that the original purpose of the article cannot be achieved, which may cause a serious accident.

Means for removing such dust, oil stains, and water (for example, wiping, removal with a wiper) may cause fine scratches on the surface. In addition, foreign particles that accompany dust, oil stains, water, etc. may make the surface scratches more remarkable.

Further, it is well known that when water adheres to the glass surface, the glass component is eluted into the water and the surface is eroded (a phenomenon called so-called burning). If it is rubbed strongly to remove this burn, fine unevenness is likely to occur. The see-through part, which consists of glass that is severely burnt or glass that has fine irregularities on its surface, has its original function deteriorated, and light scattering is severe on the surface, which causes inconvenience in securing a visual field. Not only that, but it is also a safety issue.

Dust, dirt, and water have a harmful effect on the surface of transportation equipment articles to promote damage, pollution, coloring, corrosion, etc., and electrical, mechanical and mechanical properties of transportation equipment articles.
It may also induce changes in optical properties and the like. This kind of adverse effect is not limited to articles for transportation equipment, but is a problem in various fields such as articles for construction / construction equipment and articles for electric / electronic devices.

From the above, the property of preventing the adhesion of dust, dirt, and water droplets, or the property of facilitating the removal when they adhere (hereinafter, simply referred to as antifouling property).
There is a strong demand for a technique for imparting a metal to the surface of a substrate.

As a method of imparting antifouling property, a method of directly applying a surface treatment agent such as silicone wax or silicone oil made of organopolysiloxane and a surfactant has been proposed as a method for imparting antifouling property.

However, the conventional surface treatment agents have a drawback that the adhesion of the treatment agent itself to the substrate is low, and the long-term sustainability of antifouling property cannot be satisfied, and the application range is limited. .

Further, it is desirable that the antifouling property can be imparted not only to new articles to be manufactured in the future, but also to articles already used, articles whose performance is deteriorated after treatment, and the like. However, when applying to all of these articles, it is necessary to impart antifouling property to each part only by directly treating at room temperature. For example, when treating a commercially available automobile windshield, it is impossible to replace the windshield of each automobile and heat-treat it for economical reasons. Further, it is practically impossible to bake the entire automobile after coating. Therefore, there is a problem that it is difficult to cope with the conventional treating agent and the cost is too high.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a surface treatment agent which can be treated at room temperature and can impart excellent antifouling property. Another object of the present invention is to provide a base material having antifouling properties and excellent abrasion resistance, chemical resistance, and weather resistance.

[0013]

The present invention has the general formula (A)
The present invention provides a surface treatment agent comprising: and a substrate treated with the surface treatment agent.

[0014]

Embedded image (R ¹ ) _a (R ² ) _b (Z ¹ ) _3-ab SiO- [Si (R ³ ) _c (R ⁴ ) _d (Z ² ) _2-cd O] _n -Si (R ⁵ ) _e (R ⁶ ) _f (Z ³ ) _3-ef (A) However, in the general formula (A), R ^{1 to} R ⁶ are each independently a hydrogen atom or an organic group (provided that at least one is Organic group), Z ^{1 to} Z ³ are independently an isocyanate group or a hydrolyzable group, and a to f are 0, 1, or 2 independently.
And 1 ≦ a + b ≦ 3, 0 ≦ c + d ≦ 2, 1 ≦ e +
f ≦ 3, 2 ≦ a + b + c + d + e + f ≦ 7, n
Is an integer of 0 or more.

Hereinafter, the compound represented by the general formula (A) will be referred to as compound A. When R ^{1 to} R ⁶ of the compound A are monovalent organic groups, they may be organic groups containing a halogen atom, a functional group, a linking group or the like. As the organic group, a hydrocarbon group or an organic group containing a halogen atom (hereinafter referred to as a halogenated organic group) is preferable. The carbon number of the organic group is 1 to
30 is preferred.

As the hydrocarbon group, an aliphatic hydrocarbon group,
Any of aromatic hydrocarbons may be used, and aliphatic hydrocarbon groups are preferable. As the monovalent aliphatic hydrocarbon group, an alkyl group, an alkenyl group, a cycloalkyl group and the like are preferable, and an alkyl group is particularly preferable, and specific examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. . The aromatic hydrocarbon group is preferably an aryl group or the like.

The halogen atom of the halogenated organic group is preferably a chlorine atom, a fluorine atom or a bromine atom, of which a chlorine atom and a fluorine atom are preferable, and a fluorine atom is particularly preferable.

As the halogenated organic group, a halogenated hydrocarbon group is preferable, and a halogenated alkyl group is particularly preferable. Examples of the halogenated alkyl group include a chloroalkyl group, a fluoroalkyl group and a chlorofluoroalkyl group.

The halogenated organic group is preferably a polyfluoro organic group in which two or more hydrogen atoms of the organic group are replaced by fluorine atoms. The polyfluoroorganic group is preferably a polyfluorohydrocarbon group, and particularly preferably a polyfluorohydrocarbon group in which two or more hydrogen atoms of the above hydrocarbon group are substituted with fluorine atoms.

As the polyfluorohydrocarbon group, a polyfluoroalkyl group is particularly preferable. The polyfluoroalkyl group means a group in which two or more hydrogen atoms of the alkyl group are substituted with fluorine atoms. In the following, the polyfluoroalkyl group will be referred to as R _f group.

The R _f group preferably has 3 to 18 carbon atoms. R
_{The f} group may have either a linear structure or a branched structure. As the ratio of fluorine atoms in the R _f group,
Preferably 60% or more (the number of hydrogen atoms in the alkyl group of the same number of carbon atoms corresponding to _the R _f group) (R _f number of fluorine atoms in the group) /, if in particular 80% or more.

The R _f group may contain an etheric oxygen atom, a sulfur atom or the like. For example, a polyfluorooxaalkyl group, a polyfluorothioalkyl group and the like can be mentioned. Examples of the polyfluorooxaalkyl group include a group containing a polyfluoroethyleneoxy moiety and a polyfluoropropyleneoxy moiety, a group containing a polyfluoroethyloxy moiety and a polyfluoropropyloxy moiety, and the like. Examples of the polyfluorothioalkyl group include a group containing a polyfluoroethylenethio moiety or a polyfluoropropylenethio moiety, a group containing a polyfluoroethylthio moiety or a polyfluoropropylthio moiety, and the like.

The R _f group is preferably a perfluoroalkyl group in which all the hydrogen atoms in the R _f group are substituted with fluorine atoms, a group having a perfluoroalkyl moiety, or a group having a perfluoroalkylene moiety. The perfluoroalkyl group or the perfluoroalkyl moiety preferably has 3 to 21 carbon atoms, and the perfluoroalkylene moiety preferably has 2 to 18 carbon atoms.

Particularly, the R _f group is preferably a group having a structure in which the above-mentioned perfluoroalkyl moiety and an alkylene group are linked, and particularly C _a F _{2a + 1} (CH ₂ ) _b- (where a is
Is an integer of 3 to 21, b is an integer of 1 to 6, particularly 2
Is preferred. R _f group represented by the formula () is preferable.

Further, R ^{1 to} R ⁶ of the compound A may be an organic group containing a functional group. Examples of the functional group include a hydroxyl group, an amino group, a mercapto group and a carboxyl group. The number of functional groups is not particularly limited, and is usually 1 to 2 and preferably 1 in the usual case.

Further, R ^{1 to} R ⁶ of the compound A may be an organic group containing a linking group. As the linking group, a divalent linking group is preferable, and an ester bond, an ether bond, a thioether bond, an imino bond, an amide bond, a urethane bond,
Alternatively, a divalent linking group containing these linking groups is preferable.

R ^{1 to} R ⁶ of compound A may be the same or different and each represents hydrogen or the above organic group, and at least one is an organic group. The number of organic groups is preferably 4 or more, and particularly preferably all are organic groups.

Further, the organic group preferably contains a hydrophobic organic group. As the hydrophobic organic group, a polyfluoro organic group or a long chain hydrocarbon group is preferable. As the polyfluoro organic group, a polyfluorohydrocarbon group is preferable, and an R _f group is particularly preferable.

As the long-chain hydrocarbon group, a straight-chain hydrocarbon group having 6 or more carbon atoms is preferable, and an alkyl group having 6 or more carbon atoms is particularly preferable.

Of the number of organic groups in the compound A, the number of hydrophobic organic groups is preferably a majority or more, and particularly preferably all.

Z ^{1 to} Z ^{3 in} compound A may be the same or different and each represents an isocyanate group or a hydrolyzable group. There is an idea that the isocyanate group is one kind of hydrolyzable group, but in the present invention, the isocyanate group and the hydrolyzable group are different groups. The isocyanate group and the hydrolyzable group are both very important structural units for improving the adhesion to various substrates when the compound A is treated on the substrate. The term "adhesion" as used herein means a state in which compound A and a base material are chemically and physically bonded.

As the hydrolyzable group, an alkoxy group,
Examples of the halogen atom (chlorine, bromine, iodine), acyloxy group, alkoxy-substituted alkoxy group, aminoxy group, amido group, ketoximate group and the like, alkoxy group,
A halogen atom is preferred. The number of carbon atoms of the hydrolyzable group is preferably 8 or less, particularly 4 or less. Most preferably,
It is an alkoxy group having 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group.

Z ^{1 to} Z ³ in the compound A are not particularly limited and can be appropriately selected depending on the purpose of use. Further, Z ^{1 to} Z ³ may be the same or different, and the same case is preferable from the viewpoint of easiness of synthesis.

When Z ^{1 to} Z ³ are different, a hydrolyzable group and an isocyanate group may coexist in the molecule, an isocyanate group and a chlorine atom may coexist, or different hydrolyzable groups may coexist. May be. However, in consideration of the reactivity of the compound A, Z ^{1 to} Z ³ of the compound A,
It is preferable that at least one is an isocyanate group, and in particular, from the viewpoints of adhesion to the substrate, work stability during processing, and the like, it is preferable that all of Z ^{1 to} Z ³ are isocyanate groups.

In the following, compound A having a structure in which at least one isocyanate group is present in the molecule of compound A and the isocyanate group is directly bonded to the silicon atom is referred to as isocyanate compound A.

In the isocyanate compound A, since the reactivity of the isocyanate group is very high, it is considered that most of them are chemically bonded to the surface of the substrate when treated at room temperature. That is, it is considered that the isocyanate group is changed in the bonded state. For example, it is considered that the isocyanate group reacts with the silanol group on the glass surface, and that the silanol group formed by elimination of the isocyanate group reacts.

In the compound A, a to f each represent 0, 1 or 2 and 1≤a + b≤3, 0≤.
c + d ≦ 2, 1 ≦ e + f ≦ 3, 2 ≦ a + b + c + d + e
+ F ≦ 7. In the compound A, it is preferable that the number of the isocyanate groups and / or the hydrolyzable groups directly bonded to one silicon atom is large from the viewpoint of adhesion to the base material, and particularly, the case where the number of isocyanate groups is large is preferable.
The number of isocyanate groups is preferably such that (the number of isocyanate groups in the isocyanate compound A) / (the number of silicon atoms in the isocyanate compound A) is 1 or more.

Further, n represents an integer of 0 or more. The upper limit of n is not limited and can be appropriately determined according to the purpose. When n is too large, workability during treatment is deteriorated and practicality is lowered. Therefore, n is preferably 0 to 5, particularly preferably 0 to 3, and further preferably 0.

When n is 0, the compound A is preferably a compound represented by the following general formula (A2) or general formula (A3).

[0040]

Embedded image (R _f ¹ ) (OCN) ₂ SiOSi (R _f ² ) (NCO) ₂ (A2) However, in the general formula (A2), R _f ¹ and R _f ² are
Each independently represents a polyfluoroorganic group.

The compound represented by the general formula (A2) is referred to as compound A2 below. R _f ¹ and R _f ² of the compound A2 may be the same or different, and the same case is preferable. As the polyfluoro organic group, an R _f group is preferable, and a perfluoroalkyl group or a group having a perfluoroalkyl moiety is particularly preferable.
Particularly, as R _f ¹ and R _f ² , the same C _a F as described above is used.
_{2a + 1 (CH 2) b} - ( wherein, a is an integer of 3 to 21, b is an integer from 1 to 6, particularly 2 is preferred.)
R _f groups having a perfluoroalkyl moiety represented by are preferred.

[0042]

Embedded image (R _f ³ ) (OCN) ₂ SiOSi (NCO) ₃ (A3) However, in the general formula (A3), R _f ³ represents a polyfluoroorganic group.

The compound represented by formula (A3) will be referred to as compound A3. As the polyfluoro organic group, an R _f group is preferable, and a perfluoroalkyl group or a group having a perfluoroalkyl moiety is particularly preferable. R _f ³ also has the same _Ca F _{2a + 1} (CH ₂ ) _b − as described above.
(Here, a is an integer of 3 to 21, b is an integer of 1 to 6, and 2 is particularly preferable.) A R _f group having a perfluoroalkyl moiety is preferable.

The compound A in the present invention is at least 2
It is a compound having two siloxane bonds, and it is presumed that during the treatment, a reaction between isocyanate groups or hydrolyzable groups occurs between molecules of the compound A to form a siloxane bond. Therefore, it is considered that the film obtained from the treatment agent of the present invention has extremely high crosslinkability and denseness, which contributes to the high mechanical strength and chemical stability of the film.

Further, the compound A is a substance having a low surface free energy, and in order to reduce the frictional resistance on the surface, the free state of the compound A, which is present only partly in the coating, moves through the extreme surface layer. It is considered that the wear resistance is good.

Specific examples of the compound A are shown in (A-1) to (A-151), but are not limited thereto. However, (A
In the formulas -1) to (A-151), Z represents an isocyanate group or a hydrolyzable group. R is an organic group, R _f
Represents an R _f group, and Ph represents a phenyl group. n represents an integer of 0 or more.

[0047]

[Chemical 10]

[0048]

[Chemical 11]

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

Embedded image

[0052]

[Chemical 15]

[0053]

Embedded image

[0054]

[Chemical 17]

[0055]

Embedded image

[0056]

[Chemical 19]

[0057]

Embedded image

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

[0060]

[Chemical formula 23]

[0061]

[Chemical formula 24]

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

[0064]

[Chemical 27]

[0065]

[Chemical 28]

As the compound A of the present invention, one or more of the above compounds can be used.

The surface-treating agent of the present invention may be composed of only the compound A, but it is usually preferable to include the organic solvent together with the compound A.

The organic solvent is not particularly limited and is preferably an organic solvent which dissolves or uniformly disperses the compound A of the present invention, and particularly halogenated hydrocarbons, acetic acid esters, aromatic hydrocarbons and ketones. , Various kinds of solvents such as ethers are adopted, and particularly 1,1,1,2,2-pentafluoro-3,3-dichloropropane (R-225c
a), 1,1,2,2,3-pentafluoro-1,3-
Fluorinated hydrocarbons such as dichloropropane (R-225cb) are preferred. The organic solvent having a reactive hydrogen atom is not desirable because it reacts with the isocyanate group and the like in the compound A. At least one organic solvent is used.

The mixing ratio of the organic solvent and the compound A is such that the amount of the compound A is 100 parts by weight of the organic solvent for reasons such as coatability (workability), stability, coating thickness, and economical efficiency. About 0.1 to 30 parts by weight is preferable.

The surface treating agent of the present invention may contain other compounds, additives and the like depending on the purpose. In particular, in the surface treatment agent of the present invention, as another compound, it is preferable to have another isocyanate silane compound or a silane compound having a hydrolyzable group in order to enhance the durability and durability of the treatment effect, and particularly It is preferable to include the compound B represented by the general formula (B).

[0071]

Embedded image (R ⁷ ) _p (R ⁸ ) _q (R ⁹ ) _r Si (NCO) _4-pqr (B) However, in the general formula (B), R ^{7 to} R ⁹ may be the same. They may be different, each represents a hydrogen atom or an organic group having 1 to 30 carbon atoms, and p, q, and r are respectively
0, 1, 2, or 3, and 0 ≦ p + q + r ≦
It is 3.

However, when the compound A and the compound B are mixed, the weight% of the compound A is preferably 50% or more. The reason for this is that if the weight% of compound A is less than 50%, the effect of the present invention is difficult to be exhibited.

As the compound B, (B-1) to (B-3)
The compound of 6) can be exemplified, but not limited thereto.
However, in the following chemical formula, R _f represents an R _f group.
R'represents an organic group.

[0074]

Embedded image

[0075]

[Chemical 31]

[0076]

Embedded image

The additive may be selected in consideration of the reactivity and compatibility with each component, and ultrafine particles of various metal oxides, various resins and the like can be added. Further, if coloring is required, addition of dyes, pigments, etc. does not interfere. These additives are added in an amount of 0.1-2 with respect to 100 parts by weight of compound A.
0 parts by weight is preferred. If the amount of the additive is excessive, the antifouling property, abrasion resistance and the like of the surface treating agent of the present invention are deteriorated, which is not desirable.

Further, if conductivity is required, addition of a material (tin oxide, ITO, zinc oxide, etc.) capable of obtaining a resistance suitable for the purpose does not cause any problem. The amount of these additives added may be determined according to the desired resistance value and material.

The substrate to be treated with the surface treatment agent of the present invention is not particularly limited, and includes metals, plastics, ceramics, glass, other inorganic materials and organic materials or combinations thereof (composite materials, laminated materials, etc.). Etc. can be applied. In addition, the surface of the substrate is not only the surface of the substrate itself, but also the surface of a coating film such as a coating metal, or the surface of a surface-treated glass (for example, a sol-gel film, a sputter film, a CVD film, a vapor deposition film, etc.). It may be a surface made of a material different from the base material itself (e.g., the surface provided). The shape of the base material is not particularly limited. For example, it may be of any shape depending on the purpose, such as a flat surface or one having a curvature on the whole surface or a part thereof.

Before the treatment with the treatment agent of the present invention, the substrate may be subjected to a pretreatment according to the purpose. For example, a pretreatment such as an acid treatment with diluted hydrofluoric acid or hydrochloric acid, an alkali treatment with an aqueous solution of sodium hydroxide or potassium hydroxide, or a discharge treatment such as plasma irradiation may be performed. In addition, the base material itself may be treated without pretreatment.

The method of treating the substrate with the treating agent of the present invention is not particularly limited. Usually, it can be carried out by a method of applying the treatment agent of the present invention to the surface by a usual treatment method. Examples of the coating method include various methods such as brush coating, flow coating, spin coating, dip coating and spray coating. Furthermore, an antifouling film can be formed by drying in air or nitrogen air.

Any of the above treatments can be carried out at room temperature, preferably at 20 to 30 ° C. Also, the drying time is from 5 minutes
It is about 5 hours, preferably 10 minutes to 2 hours. The treating agent of the present invention is an excellent treating agent capable of forming a coating film having desired physical properties on the surface of a substrate only by applying at room temperature. However, you may heat for the purpose of speeding up a drying rate. When heating, the temperature and time for maintaining the heat resistance of the base material may be set. It is also preferable to leave it to dry in an environment with high humidity (for example, 50% or more).

The thickness of the film formed by treating the substrate with the treating agent of the present invention is the solid content concentration in the treating agent,
It is appropriately controlled according to coating conditions, heating conditions, etc., and is not particularly limited. Usually, in order to exhibit the antifouling property, theoretically the film thickness of the coating film should be a monomolecular layer or more, and from the viewpoint of economic effect, it is preferably 2 μm or less.

Furthermore, since the coating film obtained from the treatment agent of the present invention has a low refractive index and a low refractive index, low reflectivity can also be imparted. When it is desired to impart not only antifouling property but also low reflectivity to the substrate, it is preferable to control the film thickness of the film to a film thickness that causes optical interference.

The treatment agent of the present invention has the advantage of exhibiting its performance at room temperature treatment. Further, since no special pre-treatment or post-treatment is required, the treatment can be easily performed. Therefore, it is possible to process not only a new substrate but also a substrate already used for some purpose.

Further, the treatment agent of the present invention is also used for restoration when the performance of the coating is deteriorated due to a lapse of time or a problem after the treatment agent of the present invention or another treatment agent is treated. Can be used. It can also be used partially. That is, the treatment agent of the present invention is an extremely excellent treatment agent which can be applied and developed in a wide range which has never been obtained.

Further, the following film constitution has been found as a method for further improving the effect of the surface treating agent of the present invention.

One of them is a base material having at least two surface treatment layers, which is the outermost layer of the surface treatment layer.
The layer is a layer obtained by treating with a treating agent containing compound A, and the second layer, which is a lower layer in contact with the outermost layer, is a treating agent containing a compound (C) capable of forming a heat resistant polymer thin film. A surface-treated substrate, which is a layer obtained by treatment.

The other one is a substrate having at least two surface-treated layers, and the first layer, which is the outermost layer of the surface-treated layer, is obtained by treating with a treating agent containing compound A. The second layer, which is a lower layer in contact with the outermost layer, is a thin film obtained by treating the surface of a substrate with a treatment agent containing a compound (C) capable of forming a heat-resistant polymer thin film and polymer fine particles. A surface-treated substrate, which is a heat-resistant polymer thin film layer formed by heating and thermally decomposing polymer particles.

Here, the treatment agent containing the compound (C) (hereinafter, simply referred to as compound C) for forming the heat resistant polymer thin film and the second layer formed by the treatment with the treatment agent will be described.

In the present invention, the compound C is used as a material for forming the second layer. The second layer has the effect of dramatically improving the durability of the first layer, which is an upper layer of the second layer, and also improving the adhesion to the base material. This second layer is usually formed on the surface of the base material. There is no problem even if there are already vapor-deposited films, sputtered films, various films obtained by a wet method, etc. on the surface of the substrate.

Examples of the above various films include an antistatic film, a transparent conductive film, an electromagnetic wave shielding film, an ultraviolet absorbing film, a heat ray absorbing film and a heat ray reflecting film, and these may be used in combination. There is no limitation on the material of various films, and Si, Zr, T
Examples thereof include films containing metal oxides such as i, Zn, Al, Sn, Sb, Pb, and Ta.

The compound C for forming the second layer is appropriately selected depending on the intended purpose without any limitation, and polymer compounds made of various commercially available materials can be used. The compound C may be a heat resistant polymer itself or a compound capable of becoming a heat resistant polymer by polymerization during treatment or the like.

The compound C is capable of forming a thin film on the surface of a substrate or the like during processing. For example, dissolved in the treatment agent ~
It is necessary that the dispersed compound C becomes a heat-resistant polymer thin film by removing the solvent and the like during the treatment. Specifically, a solution or dispersion of a heat resistant polymer itself or a compound that can be crosslinked to form a heat resistant polymer is used. Also, a solution or dispersion of a compound such as tetraalkoxysilane that can be converted into a heat resistant polymer by hydrolysis or a partially decomposed product thereof can be used.

Examples of the compound C include polyethylene resin, polypropylene resin, polystyrene resin, polyacrylic acid resin, polymethylmethacrylate resin, polyvinyl chloride resin, polyvinyl alcohol resin, polycarbonate resin, polyacetal resin, polyester resin, polyamide resin, polyimide resin. Examples thereof include fluorine resin, phenol resin, epoxy resin, silicone resin and the like.

Preferred compounds C are reactive silane compounds and their partial hydrolysates.

The reactive silane compound is used as a generic term for both of the following "hydrolyzable silane compound" and "isocyanate silane compound". The "hydrolyzable silane compound" is a compound in which at least one hydrolyzable group is bonded to a silicon atom. The “isocyanate silane compound” is a compound in which at least one isocyanate group is bonded to a silicon atom.

"Isocyanate group" means "hydrolyzable group".
As described above, in the present invention, the isocyanate group bonded to the silicon atom is not considered to be a hydrolyzable group.

The surface treated with "isocyanate silane compound" means a surface to which "isocyanate silane compound" is chemically or physically bound. Since the isocyanate group is reactive, the “isocyanate silane compound” is considered to be bonded to the surface of the layer to be treated mainly by a chemical reaction. That is, it is considered that the isocyanate group is changed in the bonded state. For example, an isocyanate group is considered to react with a silanol group on the glass surface, and a silanol group formed by elimination of an isocyanate group is also considered to react.

The "isocyanate silane compound" exhibits performances such as abrasion resistance, chemical resistance and weather resistance due to the reactivity of this isocyanate group and due to the siloxane skeleton formed by the reaction between the isocyanate silane compounds. It seems to do.

The surface treated with the "hydrolyzable silane compound" means the surface to which the "hydrolyzable silane compound" is chemically or physically bound. Since the hydrolyzable group is reactive, the "hydrolyzable silane compound" is considered to be bonded to the surface of the layer to be treated mainly by a chemical reaction. That is, it is considered that the hydrolyzable group is changed in the bound state.

The hydrolyzable group in this "hydrolyzable silane compound" is a group directly bonded to a silicon atom. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group, an aminoxy group, an amide group, and a ketoximate group. Preferably, it is a hydrolyzable group such as an alkoxy group, an alkoxy-substituted alkoxy group or an acyloxy group, which is bonded to a silicon atom by an oxygen atom. These hydrolyzable groups preferably have 8 or less carbon atoms, and particularly preferably 4 or less carbon atoms. More preferably, it is an alkoxy group having 1 to 4 carbon atoms.

The "hydrolyzable silane compound" has abrasion resistance, chemical resistance and weather resistance due to the reactivity of the hydrolyzable group and the siloxane skeleton formed by the reaction between the hydrolyzable silane compounds. It is thought that it exhibits performance such as sex.

The "hydrolyzable silane compound" may be used as it is or may be used as a partial hydrolysis product by hydrolysis. The partial hydrolysis product of the "hydrolyzable silane compound" means a compound having a silanol group or the like, which is generated by partially hydrolyzing the hydrolyzable silane compound in water or an acidic aqueous solution, or a reaction of the silanol group. Is a compound in which two or more molecules are condensed. As the acid, for example, hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid or the like can be used.

Two or more of the above reactive silane compounds may be used in combination. However, it is better to avoid mixing "isocyanate silane compound" and "hydrolyzable silane compound" together. This is because the isocyanate group and the hydrolyzable group may react with each other, and the life of the treating agent is shortened.

Preferred reactive silane compounds are compounds having 1-2 hydrolyzable groups and / or isocyanate groups directly bonded to silicon atoms. More preferred as this compound are the compound represented by the general formula (C1) (also referred to as compound C1) and the compound represented by the general formula (C2) (also referred to as compound C2).

[0107]

_{Embedded image} (Z) _3-ij (R ¹⁰ ) _i (R ¹¹ ) _j Si-Y-Si (R ¹² ) _k (R ¹³ ) _m (Z) _3-km (C1) However, in general In the formula (C1), R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ is independently a hydrogen atom, a hydroxyl group, an amino group or an organic group having 1 to 30 carbon atoms, Y is a divalent organic group, Z is an isocyanate group and / or a hydrolyzable group, i and j are independently 0, 1 or 2, 0 ≦ i + j ≦ 2, k and m are independently 0, 1 or 2, and 0 ≦ k + m ≦ 2.

[0108]

_{Embedded image} (R ¹⁴ ) _e (R ¹⁵ ) _g (R ¹⁶ ) _h Si (Z) _4-egh (C2) However, in the general formula (C2), R ¹⁴ , R ¹⁵ , and R ¹⁶ are Independently a hydrogen atom or an organic group having 1 to 30 carbon atoms (provided that at least one is an organic group), Z is an isocyanate group and / or a hydrolyzable group, and e, g and h are independently 0,
1 or 2, and 0 ≦ e + g + h ≦ 3.

The reactive silane compound for forming the second layer is firmly bonded to the first layer and the lower layer (eg, base material) by the reactivity of the isocyanate group or the hydrolyzable group. Further, the siloxane skeleton resulting from the isocyanate group or the hydrolyzable group improves abrasion resistance. Therefore, the greater the number of isocyanate groups or hydrolyzable groups directly bonded to silicon atoms per silicon atom, the better.

When the reactive silane compound is the compound C1 or the compound C2, the organic group is preferably an organic group which is not a fluorine atom-containing organic group, particularly a hydrocarbon group. A lower alkyl group and an alkylene group having 6 or less carbon atoms are most preferable.

When the compound A used in the first layer has an organic group having a fluorine atom, the organic groups of the compounds C1 and C2 may be those having a relatively lower hydrophobicity. In some cases, it may be a long-chain hydrocarbon group.

In particular, considering the adhesion to the first layer and the lower layer (for example, the base material), the larger the number of the isocyanate group or the hydrolyzable group bonded to the silicon atom, the better,
In the compound C1, i = j = k = m = 0 in the formula (C1).
Of the compound C2 in the formula (C2) is e = g
Compounds with = h = 0 are preferred.

Specific examples include tetraisocyanate silane and tetraalkoxy silane.

Specific examples of the compound C1 include compounds represented by the formula (C-
1) to (C-87) and the like. Specific examples of the compound C2 include compounds represented by the formula (B-
1) to (B-36) and the like. In addition, the compound which substituted the isocyanate group in the illustrated compound by the hydrolyzable group can be illustrated similarly. P in these formulas represents an integer, and 2-8 are preferable.

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

[Chemical 38]

[0119]

[Chemical Formula 39]

[0120]

[Chemical 40]

[0121]

Embedded image

[0122]

Embedded image

[0123]

[Chemical 43]

As the treating agent for forming the second layer of the present invention, it is desirable to use a solution or dispersion containing a reactive silane compound as an essential component. This treating agent contains a solvent,
In addition to the dispersant, other additives can be added.

Other compounds and additives may be added to the treating agent containing the reactive silane compound depending on the purpose. The additives and the like may be selected in consideration of the reactivity and compatibility with each component, and for example, fine particles of various metal oxides such as silica, alumina, zirconia, titania, and various resins can be added. If coloring is required, addition of dyes, pigments, etc. does not interfere. The addition amount is 0.01 to 20 relative to the total weight of other components.
It may be about wt%, and excessive addition thereof is not desirable because it deteriorates wear resistance and the like.

Further, if conductivity is required, a material (tin oxide, ITO, zinc oxide, etc.) capable of obtaining resistance according to the purpose may be added. The amount of these additives added may be determined according to the desired resistance value and material.

The above composition may be applied directly by a method such as hand wiping. It may be dissolved, dispersed or diluted with an organic solvent to prepare a solution form for use.

In the solution with this organic solvent, the total amount of each component contained is the moldability (workability) of the coating, the stability,
It is determined in consideration of the coating thickness and economical efficiency, and it is preferable that the amount is adjusted to 0.1 to 30% by weight.

As the organic solvent, various organic solvents such as acetic acid esters, aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethers and alcohols can be applied. However, when the reactive silane compound has an isocyanate group, a compound having a reactive functional group (such as a hydroxyl group) is not desirable. Therefore, alcohols are not suitable for the isocyanate silane compound, but there is no particular limitation for the hydrolyzable silane compound. The diluent solvent is not limited to one type, and a mixed solvent of two or more types can also be used.

Further, in the present invention, the second layer can be formed by the treating agent containing the compound C and the fine polymer particles.

As the polymer fine particles used in this case, polyethylene resin, polypropylene resin, polystyrene resin, polyacrylic acid resin, polymethylmethacrylate resin, polyvinyl chloride resin, polyvinyl alcohol resin,
Examples thereof include polycarbonate resin, polyacetal resin, polyester resin, polyamide resin, polyimide resin, fluororesin, phenol resin, epoxy resin, and silicone resin. The material of the polymer fine particles may be one kind selected from these exemplified compounds, or a mixture of two or more kinds.

The average particle size of the fine polymer particles is not particularly limited, and is preferably in the range of 1 to 1000 nm from the viewpoint of film strength. In particular, when importance is attached to transparency, the average particle size is 500 nm or less in order to prevent light scattering.
It is particularly preferably 200 nm or less. The particle shape is not particularly limited, but is usually spherical. Of the above-mentioned materials, the material is preferably a thermoplastic resin such as polystyrene resin or polymethylmethacrylate resin.

The ratio of the polymer fine particles to the total of the polymer fine particles and the compound C is not particularly limited, and if the blending amount of the polymer fine particles is too high, the mechanical strength of the coating film formed after thermal decomposition is lowered, and therefore 80% by weight. % Or less, and if it is too low, the effect of adding fine polymer particles is difficult to be expressed, so that it is preferably 5% by weight or more. More preferably 5-5
0% by weight.

The heat resistant polymer formed by the compound C needs to be a material having a thermal decomposition temperature higher than the thermal decomposition temperature of the polymer fine particles. A material that does not chemically or physically change when the polymer fine particles are thermally decomposed is particularly preferable.
In particular, the heat resistant polymer preferably has a thermal decomposition temperature higher by at least 50 ° C. than the polymer particles.

From the viewpoint of work, it is preferable to use the compound C forming the second layer after diluting the polymer fine particles and the binder with a solvent. Examples of the solvent used at this time include the above-mentioned organic solvents.

No special pretreatment is required for the surface treatment of the substrate. However, there is no particular problem according to the purpose, and for example, acid treatment with diluted hydrofluoric acid, hydrochloric acid or the like, alkali treatment with sodium hydroxide aqueous solution or the like, or discharge treatment with plasma irradiation or the like can be performed.

The formation of the second layer is not particularly limited, and a liquid material usually composed of the prepared organic solvent containing the compound C is applied to the surface by a conventional treatment method (for example, brush coating, flow coating, spin coating). Coating, dip coating, spray coating, flexo, various printing methods such as screen, etc.),
Dry in air or nitrogen.

Drying at room temperature is sufficient. When heating and drying, the temperature and time may be set in consideration of the heat resistance of the base material.

Further, when fine polymer particles are used as the treatment agent for forming the second layer, the heat treatment causes the fine polymer particles to be thermally decomposed to form an uneven surface. Therefore, the heating temperature may be determined according to the spherical polymer compound, the heat resistance of the substrate, and the like. Usually, it is processed in the range of 100 ° C to 800 ° C.

The thermal decomposition of the fine polymer particles by the heat treatment does not have to be complete, and the effects of the present invention are sufficient even if they partially remain, for example, inside the heat-resistant polymer thin film. .

The thickness of the second layer is not particularly limited, but may be extremely thin. The preferable film thickness is 2 μm or less. The lower limit is the monolayer thickness. A too thick film thickness is not preferable in terms of appearance quality and economy.

The substrate used in the present invention includes
A base material made of a transparent material such as glass or plastics is preferable. Further, it is preferably used as an article for transportation equipment and an article for construction / construction.

The article for transportation equipment is an outer plate of transportation equipment such as trains, buses, trucks, automobiles, ships, and aircrafts,
It refers to exterior members such as window glass, mirrors, surface materials for display devices, interior members such as surface materials for instrument panels, and other parts and components used or used in transportation equipment.

For example, body of a train, window glass, pantograph, etc., body of automobile, bus, truck, windshield, side glass, rear glass, mirror, bumper, body of ship, window glass, body of aircraft, etc. Window glass etc. can be illustrated.

The article may consist only of the surface-treated substrate, or may incorporate the surface-treated substrate. For example, there is a window glass for an automobile as the former and a rearview mirror member for an automobile in which a glass mirror is incorporated as the latter.

In such a substrate or article, the water droplet removability repels water droplets adhering to the surface, and in particular, during operation, the water droplets rapidly move on the surface due to the interaction with the received wind pressure, and do not accumulate as water droplets. , The adverse effects caused by water can be eliminated. In particular, when used in a transparent field such as various window glasses, it is very easy to secure a field of view due to the scattering of water droplets, which leads to improvement of vehicle safety.

Further, even in an environment where water droplets freeze, it does not freeze, and even if it freezes, thawing is extremely fast. Furthermore, since there are almost no water droplets attached, the number of regular cleaning operations can be reduced, and cleaning is extremely easy, which is very advantageous in terms of aesthetic protection.

The building / building article is an article attached to a building, an article already attached to a building, a building article that is not attached to a building and is used with it, or furniture. , Refers to furniture and other building equipment.

[0149] For example, window glass, various roofs including roof glass plates and roofs, door glass plates and doors in which they are fitted, partition glass plates, greenhouse glass plates and greenhouses, transparent plastics plates. There are window materials, roof materials, and the like using ceramics, wall materials made of ceramics, cement, metal, and other materials, mirrors and furniture having the same, and glass for display shelves and showcases.

The article may consist only of the surface-treated substrate, or may incorporate the surface-treated substrate. For example, the former is a glass plate for windows, and the latter is furniture incorporating a glass mirror.

In such a surface-treated substrate,
Due to the water drop removability, the water drops that come into contact with the surface are repelled and hardly adhere, and even if they adhere, the amount thereof is small and the adhered water drops can be easily removed. Further, it does not freeze even in an environment where water drops freeze, and even if it freezes, thawing is extremely fast. Furthermore, since there are almost no water droplets attached, the number of regular cleaning operations can be reduced, and cleaning is extremely easy, which is very advantageous in terms of aesthetic protection.

[0152]

EXAMPLES The present invention will be specifically described with reference to examples, but the invention is not limited thereto. The evaluation methods of the antifouling property and the antifouling durability in the examples are as follows.

[Evaluation Method of Antifouling Property] a) The contact angle of water was measured. B) The contact angle of hexadecane was measured. C) The fingerprint removability was evaluated by the following method. That is, a fingerprint of a hand is attached to the treated surface, wiped 20 times with a cotton cloth and the appearance is inspected. A: Completely clean oil stains can be wiped off, B: Some oil stains remain, C: Some oil stains remain. It was evaluated according to the standard. D) Water drop residual property was evaluated by the following method. That is, after vertically spraying water on the entire surface of a vertically standing sample from a nozzle held at a distance of 20 cm for about 1 hour, water droplets remaining on the surface are visually observed, and A: no water remains on the sample surface, B: It was evaluated based on the criteria that a small amount of water remained on the sample surface, C: considerable water droplets remained on the sample surface, and D: water spreads wet on the sample surface.

[Evaluation Method of Antifouling Durability] C) After dipping in boiling water for 3 hours, c) fingerprint removability and d) water drop residual property were evaluated.

Example 1 C ₈ F ₁₇ C ₂ H ₄ Si (NCO) ₃ 1 was placed in a flask equipped with a stir bar and a thermometer.
After adding 00 g and 900 g of dehydrated ethyl acetate in advance and replacing the atmosphere in the flask with dry nitrogen gas, the mixture was well stirred at 25 ° C. for 30 minutes.

2.98 g of distilled water was gradually added dropwise to this solution over 3 hours. The solution was maintained at 25 ° C., stirred for 3 days and night, and then ethyl acetate was removed by distillation. Further, the remaining powder was washed with ethyl acetate and then well dried to obtain a reaction product.

Mass spectrometry was performed on the resulting reaction product. For mass spectrometry, a SX-102A device manufactured by JEOL Ltd. was used.
I ⁺ method (reagent gas NO), temperature rise is 50 ° C to 260 ° C
(32 ° C./min). As a result of the analysis, Fig. 1
1164 (molecular weight of the reaction product 1134+
A peak was confirmed in the NO molecular weight 30). Further, when the infrared spectroscopic spectrum of the obtained reaction product was measured,
As shown in FIG. 2, an NCO peak was confirmed at 2290 cm ⁻¹ .

From the above points, the reaction product is (C ₈ F ₁₇ C ₂
H ₄ ) (OCN) ₂ SiOSi (C ₈ F ₁₇ C ₂ H ₄ ).
It was confirmed to be (NCO) ₂ .

A flask equipped with a stir bar and a thermometer was charged with (C ₈ F ₁₇ C ₂ H ₄ ) (OCN) ₂ SiOSi.
2.0 g of the compound (a-1) having a structure of (C ₈ F ₁₇ C ₂ H ₄ ) (NCO) ₂ and 98.0 g of dichloropentafluoropropane were added. While maintaining the liquid temperature of this solution at 25 ° C., stirring was continued for one day to obtain a treating agent 1.

Prewashed glass plate (10 cm x
1 cc of Treatment Agent 1 is dropped onto 10 cm × 2 mm thick, and J
A sample glass was prepared by spreading it with a K wiper (product of Tojo Kimberley Co., Ltd.) in the same way as waxing an automobile and leaving it for one day. Table 1 shows the results of evaluating the antifouling property and antifouling durability of the sample glass obtained as described above.

[Comparative Example 1] Table 1 shows the results of the same evaluation of the glass plate of Example 1 without any treatment.

[Examples 2 to 7 and Comparative Examples 2 to 4] The same as Example 1 except that the compound (a-1) in Example 1 was replaced by the compound and amount (g) shown in Table 2. A treatment liquid was prepared by using the treatment liquid, and a sample glass was prepared and evaluated in the same manner as in Example 1 using the treatment liquid. The evaluation results are shown in Table 3.

[Examples 8 to 11] Instead of the glass plate of Example 1, an acrylic plate (AC), a polycarbonate plate (PC), a CR39 polymer plate (CR), and an aluminum plate (AL) were used as base materials. The same treatment as in Example 1 was carried out except that it was used and evaluated. The results are shown in Table 4.

[Comparative Examples 5 to 8] Instead of the glass plate of Comparative Example 1, an acrylic plate (AC), a polycarbonate plate (P
C), a CR39 polymer plate (CR), and an aluminum plate (AL) were used as the base material, and the evaluation was performed in the same manner as in Comparative Example 1. The results are shown in Table 4.

[Examples 12 to 14] The sample glass of Example 1 was heat-treated at 100 ° C, 200 ° C, and 300 ° C, and evaluated in the same manner as in Example 1.
The results are shown in Table 5.

Example 15 Si (NCO) ₄ 0.1 was placed in a three-necked flask equipped with a stir bar and a thermometer.
g and 99.9 g of ethyl acetate were added, and the mixture was stirred for 1 hour. While maintaining the temperature of this solution at 25 ° C., stirring was continued for one day to obtain a treating agent 15.

1 cc of a solution of the treating agent 15 was dropped on a glass plate (10 cm × 10 cm × thickness 3 mm) which had been previously polished by cerium oxide polishing, and spread with a JK wiper in the same manner as waxing an automobile. 25 this plate
It was left for 1 hour in an environment of ℃ and 50% humidity. After that, 1 cc of the solution of the treating agent 1 was dropped on the treated surface and spread with a JK wiper in the same manner as waxing an automobile. This plate was left for one day under an environment of 25 ° C. and a humidity of 50% to obtain a test piece. Table 6 shows the results of evaluation of this test piece performed in the same manner as in Example 1.

Example 16 Si (NCO) ₄ 0.1 was placed in a three-necked flask equipped with a stirring bar and a thermometer.
g, (NCO) ₃ SiC ₂ H ₄ Si (NCO) ₃ 0.1
g and 99.8 g of ethyl acetate were added, and the mixture was stirred for 1 hour. While maintaining the temperature of this solution at 25 ° C., stirring was continued for one day to obtain a treating agent 16.

Treating Agent 15 in Example 15 was treated with Treating Agent 1
The test and evaluation were performed in the same manner as in Example 15 except that the number was changed to 6. The results are also shown in Table 6.

Example 17 605.3 g of hexylene glycol was placed in a container equipped with a stirrer and a thermometer, then 43.8 g of Si (OC ₂ H ₅ ) ₄ 43.7 g of 1% by weight hydrochloric acid aqueous solution. Are added in sequence and stirred at 30 ° C for 3
The treatment was carried out for 0 minutes and left for 1 day and night to obtain a treating agent 17.

A treatment agent 17 was applied by a flexographic printing method to a glass plate (10 cm × 10 cm × thickness 3 mm) which had been polished and cleaned with cerium oxide in advance, and the treatment was performed in a muffle furnace at 60
Heat treatment was performed at 0 ° C. for 10 minutes. After the heat treatment, the plate was taken out from the muffle furnace and cooled to room temperature. Next, 1 cc of Treatment Agent 1 was dropped on the treated surface of this plate and spread with a JK wiper (manufactured by Tojo Kimberley Co., Ltd.) in the same way as waxing an automobile. This plate was left for one day in an environment of 25 ° C. and a humidity of 50% to obtain a test piece. About this test piece Example 1
Table 6 shows the results of the same evaluations as above.

Example 18 605.3 g of hexylene glycol was placed in a container in which a stir bar and a thermometer were set, and then 43.8 g of Si (OC ₂ H ₅ ) ₄ 43.7 g of 1% by weight hydrochloric acid aqueous solution. Then, 30.0 g of polystyrene fine particles having an average particle diameter of 70 nm were sequentially added, and the mixture was stirred at 30 ° C. for 30 minutes.
The treatment was carried out for 1 minute and left overnight to obtain a treating agent 18.

Evaluation was performed in the same manner as in Example 17 except that the treating agent 18 was used instead of the treating agent 17 in Example 17. The results are shown in Table 6.

[Example 19] 605.3 g of hexylene glycol was placed in a container equipped with a stir bar and a thermometer, then 43.8 g of Si (OC ₂ H ₅ ) ₄ 43.7 g of 1% by weight hydrochloric acid aqueous solution. , 7.0 g of polymethylmethacrylate fine particles having an average particle diameter of 150 nm are sequentially added, and the temperature is 30 ° C.
After stirring for 30 minutes, the mixture was left for one day and night to obtain a treating agent 19.

Evaluation was carried out in the same manner as in Example 17 except that the treating agent 19 was used in place of the treating agent 17 in Example 17. The results are shown in Table 6.

Example 20 605.3 g of hexylene glycol was placed in a container equipped with a stirrer and a thermometer, then 43.8 g of Si (OC ₂ H ₅ ) ₄ 43.7 g of 1% by weight hydrochloric acid aqueous solution. , 28.0 g of polymethylmethacrylate fine particle dispersion liquid having an average particle diameter of 80 nm (manufactured by Soken Chemical Industry Co., Ltd .: trade name MS-300) are sequentially added, and the mixture is stirred at 30 ° C. for 30 minutes and left standing for 1 day and 20 days. Got

Evaluation was performed in the same manner as in Example 17 except that the treating agent 20 was used instead of the treating agent 17 in Example 17. The results are shown in Table 6.

Example 21 935.0 g of isobutyl acetate was placed in a container equipped with a stir bar and a thermometer, and then 25.0 g of Si (NCO) ₄ and a polymethylmethacrylate fine particle dispersion liquid having an average particle size of 80 nm ( Soken Chemical Co., Ltd.
Manufactured by: MS-300, trade name, 40.0 g are sequentially added,
Stirring was carried out at 30 ° C. for 30 minutes, and the mixture was left for one day and night to obtain a treating agent 21.

Evaluation was performed in the same manner as in Example 17 except that the treating agent 21 was used in place of the treating agent 17 in Example 17. The results are shown in Table 6.

Comparative Example 9 C ₈ F ₁₇ C ₂ H ₄ Si (NC) was placed in a three-necked flask equipped with a stirring bar and a thermometer.
O) _{3 (} 2.0 g) and ethyl acetate (98.0 g) were added, and the mixture was stirred for 1 hour. While maintaining the temperature of this solution at 25 ° C., stirring was continued for one day to obtain a treating agent 22.

In Example 15, treating agent 1 was treated with treating agent 22
The tests and evaluations were performed in the same manner as in Example 15 except that the above was changed to. The results are also shown in Table 6.

[Comparative Example 10] The same tests and evaluations as in Example 20 were carried out except that the treating agent 1 was changed to the treating agent 22 in Example 20. The results are also shown in Table 6.

Comparative Example 11 C ₈ F ₁₇ C ₂ H ₄ Si (OC) was placed in a three-necked flask equipped with a stir bar and a thermometer.
H ₃ ) ₃ 2.5 g, isopropyl alcohol 72.0
g was added and the mixture was stirred for 1 hour. 0.7 g of a 1 wt% hydrochloric acid aqueous solution was added dropwise to this solution over 1 hour. The temperature of this solution is 25
While maintaining the temperature at 0 ° C., stirring was continued for 3 days to obtain a treating agent 23.

1 cc of the solution of the treating agent 15 was dropped on a glass plate (10 cm × 10 cm × thickness 3 mm) which had been previously cleaned by polishing with cerium oxide, and spread with a JK wiper in the same manner as waxing an automobile. 25 this plate
It was left for 1 hour in an environment of ℃ and 50% humidity. Then, 1 cc of a solution of the treating agent 23 was dropped on the treated surface, spread with a JK wiper in the same manner as waxing an automobile, and dried by heating at 100 ° C. for 30 minutes to obtain a test piece. The results of evaluation of this test piece performed in the same manner as in Example 15 are shown in Table 6.
Shown in

[Comparative Example 12] A treatment agent 20 was applied by a flexographic printing method to a glass plate (10 cm × 10 cm × thickness 3 mm) which had been polished and cleaned in advance with cerium oxide, and heated at 600 ° C. for 10 minutes in a muffle furnace. I went. After the heat treatment, the plate was taken out from the muffle furnace and cooled to room temperature.
Next, 1 cc of the treating agent 23 was dropped on the treated surface of this plate, and JK
A test piece was obtained by spreading with a wiper (manufactured by Tojo Kimberley Co., Ltd.) in the same way as waxing an automobile and heating and drying at 100 ° C. for 30 minutes. Table 6 shows the results of evaluation of this test piece performed in the same manner as in Example 15.

Example 22 The sample glass of Example 1 was immersed in the chemicals shown in Table 7 for 24 hours, taken out and immediately washed, and then the sample was evaluated for appearance change, fingerprint removability and water drop residual property. The results are shown in Table 7.

[Example 23] The same evaluation as in Example 22 was carried out except that the sample glass of Example 15 was used in place of the sample glass of Example 1 in Example 22. The results are shown in Table 7.

Example 24 The same procedure as in Example 22 was carried out except that the sample glass of Example 17 was used in place of the sample glass of Example 1 in Example 22, and the evaluation was carried out. The results are shown in Table 7.

[Example 25] The same evaluation as in Example 22 was carried out except that the sample glass of Example 20 was used in place of the sample glass of Example 1 in Example 22. The results are shown in Table 7.

Example 26 With respect to the sample glass of Example 1, a flannel cloth was rubbed back and forth 20000 times under a load of 1 kg. Table 8 shows the evaluation results of the antifouling property after the abrasion test.

[Comparative Example 13] The evaluation was carried out in the same manner as in Example 26 except that the sample glass of Comparative Example 2 was used in place of the sample glass of Example 1 in Example 26.
Table 8 shows the results.

Example 27 The procedure of Example 26 was repeated except that the sample glass of Example 15 was used in place of the sample glass of Example 1 in Example 26. Table 8 shows the results.

Example 28 The procedure of Example 26 was repeated, except that the sample glass of Example 17 was used instead of the sample glass of Example 1, and the evaluation was carried out. Table 8 shows the results.

Example 29 The same procedure as in Example 26 was carried out except that the sample glass of Example 20 was used in place of the sample glass of Example 1 in Example 26, and the evaluation was carried out. Table 8 shows the results.

[Embodiment 30] UV irradiation was carried out for 8 hours (70
The sample glass of Example 1 was subjected to a weather resistance test for 250 cycles, in which a cycle of a process in which the humidity exposure was 4 hours (50 ° C.) was performed. Table 9 shows the evaluation results of the antifouling property after the weather resistance test.

[Comparative Example 14] The evaluation was carried out in the same manner as in Example 30 except that the sample glass of Comparative Example 2 was used in place of the sample glass of Example 1 in Example 30.
The results are shown in Table 9.

[Example 31] The evaluation was carried out in the same manner as in Example 30 except that the sample glass of Example 15 was used in place of the sample glass of Example 1 in Example 30. The results are shown in Table 9.

[Example 32] The same evaluation as in Example 30 was carried out except that the sample glass of Example 17 was used in place of the sample glass of Example 1 in Example 30. The results are shown in Table 9.

[Example 33] The evaluation was performed in the same manner as in Example 30 except that the sample glass of Example 20 was used in place of the sample glass of Example 1 in Example 30. The results are shown in Table 9.

Example 34 The surface of a front laminated glass for automobiles was treated by the method of Example 1 and mounted on an automobile. This vehicle was subjected to a running test for 4 hours in the day for one month, and the state of dirt and dust adhering to the front surface, and the state of water drop adhering to the front surface were observed with the naked eye every day.

As a result, no stains, dust deposits, or water stains due to water droplets were found, and even if they were found, they were easily removed by wiping with a tissue paper. Also, in rainy weather, water droplets on the surface were repelled and moved quickly due to interaction with the wind pressure due to running, and the field of view was secured without using a wiper. Furthermore, in a running test under an environment (0 ° C to -5 ° C) where water droplets adhering to the untreated windshield are frozen, or water in the air is condensed to freeze the windshield. No freezing was observed at.

Next, in a more severe low temperature environment (-10 ° C.
(--15 ° C), freezing on the windshield was also observed, but the thawing was fast, and there was a significant difference compared to the untreated windshield.

[Example 35] A running test was conducted by changing the front laminated glass of Example 34 to a side glass, a rear glass and a side mirror, but the same effect as that of Example 34 was confirmed.

[Example 36] A running test was conducted in the same manner as in Example 34 except that the treatment method of Example 15 was used in place of the treatment method of Example 1, and a running test was conducted. The same effect was confirmed.

[Example 37] A running test was conducted in the same manner as in Example 34 except that the treatment method of Example 20 was used instead of the treatment method of Example 1, and a running test was conducted. The same effect was confirmed.

[Example 38] By applying the method of Example 1 to the surface of a building window glass, a coating film was formed. The window glass thus obtained was attached to the house. The state of dirt and dust adhering to the surface of the window glass, and the state of water droplet adhering to the surface of the window glass were observed with the naked eye.

As a result, no stains, dust deposits, or water stains due to water droplets were found, and even if they were rarely found, they were easily removed by gently wiping with a tissue paper. Also, in rainy weather, water drops on the surface were repelled and fell, and on a windy day in particular, it moved quickly due to the interaction with wind pressure, and the field of view was secured. Furthermore, in a test under an environment (0 ° C. to −5 ° C.) in which water droplets adhering to the untreated window glass are frozen, or moisture in the air is condensed to be frozen on the window glass, No freezing was observed.

Next, in a more severe low temperature environment (-10 ° C.
(--15 ° C), freezing was observed on the window glass, but the thawing was fast and there was a significant difference compared to the untreated window glass.

Example 39 An automobile front laminated glass, which had been used for 5 years, was polished with calcium carbonate, washed with water and dried. On the surface of the front laminated glass, 10 cc of the solution of the treating agent 1 was dropped and spread with a JK wiper in the same manner as waxing an automobile.

When a running test similar to that of Example 34 was carried out using this automobile, the same effect as that of Example 34 could be confirmed.

[Example 40] A front laminated glass of an automobile, which has been used for 5 years, was polished with calcium carbonate, washed with water and dried. 10 cc of the treatment agent 15 solution was dropped on the surface of the front laminated glass, spread with a JK wiper in the same manner as waxing an automobile, and left for 1 hour. At this time, the temperature was 19 ° C. and the humidity was 46%.

Then, the solution of the treating agent 1 is applied to the treated surface in an amount of 10 c.
c was dropped, spread with a JK wiper in the same manner as waxing an automobile, and left for 1 day.

When a running test similar to that of Example 34 was conducted using this automobile, the same effect as that of Example 34 was confirmed.

[0214]

[Table 1]

[0215]

[Table 2]

[0216]

[Table 3]

[0219]

[Table 4]

[0218]

[Table 5]

[0219]

[Table 6]

[0220]

[Table 7]

[0221]

[Table 8]

[0222]

[Table 9]

[0223]

The treatment agent of the present invention, the substrate having a film obtained from the surface treatment agent, and the article equipped with the same have the following excellent effects.

(1) The surface treating agent of the present invention can be treated at room temperature and can impart excellent antifouling property to the substrate. Therefore, it is possible not only to treat a newly manufactured article, but also to treat an already used article. Also,
Since heat treatment is not required, the necessary portion can be appropriately treated without breaking the shape of the article.

(2) The base material of the present invention, or an article equipped with them, has excellent antifouling properties, and is free from dust, dirt, water droplets, or water stains, which rarely occurs. Even if it exists, it can be easily removed, the adverse effect caused by water can be blocked, and the cleaning can be simplified.

(3) The base material of the present invention or an article equipped with them has excellent antifouling properties, and at the same time has chemical resistance, abrasion resistance and weather resistance, so that the antifouling property is maintained. Excellent and semi-permanently maintained antifouling property.

(4) The surface treating agent of the present invention can be applied not only to glass but also to a wide range of other substrates. In addition, there is no need for special pretreatment during treatment, and continuous treatment is possible, which is economically advantageous.

The above-mentioned effects cannot be expected with conventional materials, and it can be expected that the range of application thereof will be expanded to fields where the conventional materials cannot be used.

[Brief description of drawings]

FIG. 1 is a diagram showing a mass spectrometry result of a surface treatment agent according to Example 1.

FIG. 2 is an infrared spectrum of the surface treatment agent according to Example 1.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location C09K 3/18 104 // C07F 7/12 X (72) Inventor Kenji Ishizeki 1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa Address Central Research Institute, Asahi Glass Co., Ltd. (72) Inventor Yukiko Ono 543 Sanma-cho, Kanagawa-ku, Yokohama-shi, Kanagawa

Claims (15)

[Claims] 1. A surface treatment agent containing a silicone compound represented by the general formula (A). Embedded image (R ¹ ) _a (R ² ) _b (Z ¹ ) _3-ab SiO- [Si (R ³ ) _c (R ⁴ ) _d (Z ² ) _2-cd O] _n -Si (R ⁵ ) _e (R ⁶ ) _f (Z ³ ) _3-ef ... (A) However, in the general formula (A), R ^{1 to} R ⁶ are each independently a hydrogen atom or an organic group (provided that at least one is Organic group), Z ^{1 to} Z ³ are independently an isocyanate group or a hydrolyzable group, and a to f are independently 0, 1 or 2, and 1 ≦ a
+ B ≦ 3, 0 ≦ c + d ≦ 2, 1 ≦ e + f ≦ 3, and 2
≦ a + b + c + d + e + f ≦ 7, n is an integer of 0 or more. 2. The surface treating agent according to claim 1, wherein at least one of Z ^{1 to} Z ³ is an isocyanate group. 3. The surface treating agent according to claim 1, wherein the silicone compound is a silicone compound represented by formula (A2). Embedded image (R _f ¹ ) (OCN) ₂ SiOSi (R _f ² ) (NCO) ₂ (A2) However, in the general formula (A2), R _f ¹ and R _f ² are
Independently, it is a polyfluoroorganic group. 4. The surface treating agent according to claim 1, wherein the silicone compound is a silicone compound represented by the general formula (A3). Embedded image (R _f ³ ) (OCN) ₂ SiOSi (NCO) ₃ (A3) However, in the general formula (A3), R _f ³ is a polyfluoroorganic group. 5. The surface treating agent according to claim 1, which further contains a compound represented by the general formula (B). Embedded image (R ⁷ ) _p (R ⁸ ) _q (R ⁹ ) _r Si (NCO) _4-pqr (B) However, in the general formula (B), R ^{7 to} R ⁹ are independently , A hydrogen atom or an organic group having 1 to 30 carbon atoms, p, q and r are independently 0, 1, 2 or 3 and 0 ≦ p + q + r ≦ 3. 6. A base material whose surface is treated with the surface treatment agent according to claim 1. 7. A base material having at least two surface treatment layers, wherein the first layer, which is the outermost layer of the surface treatment layer, is a layer obtained by treating with the surface treatment agent according to claim 1. A substrate, wherein the second layer, which is a lower layer in contact with the outermost layer, is a layer obtained by treating with a treatment agent containing the compound (C) which forms a heat resistant polymer thin film. 8. A substrate having at least two surface-treated layers, wherein the first layer which is the outermost layer of the surface-treated layer is a layer obtained by treating with the surface-treating agent according to claim 1. The second layer, which is the lower layer in contact with the outermost layer, is a polymer obtained by heating the thin film obtained by treating the surface of the substrate with a treatment agent containing the compound (C) forming the heat-resistant polymer thin film and polymer fine particles. A base material, which is a layer formed by thermally decomposing fine particles. 9. The polymer fine particles have an average particle size of 1 to 1,000.
The substrate of claim 8 which is nm. 10. The base material according to claim 7, wherein the compound (C) is a reactive silane compound having an isocyanate group and / or a hydrolyzable group bonded to a silicon atom. 11. The compound (C) has the general formula (C1) and / or
The base material according to claim 7 or 8, which is a compound represented by (C2). [Chemical _Formula 5] (Z) _3-ij (R ¹⁰ ) _i (R ¹¹ ) _j Si-Y-Si (R ¹² ) _k (R ¹³ ) _m (Z) _3-km (C1) However, in general In the formula (C1), R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ is independently a hydrogen atom, a hydroxyl group, an amino group or an organic group having 1 to 30 carbon atoms, Y is a divalent organic group, Z is an isocyanate group and / or a hydrolyzable group, i and j are independently 0, 1 or 2 and 0 ≦ i + j ≦
2, k and m are independently 0, 1 or 2 and 0 ≦ k + m ≦
It is 2. _{Embedded image} (R ¹⁴ ) _e (R ¹⁵ ) _g (R ¹⁶ ) _h Si (Z) _4-egh (C2) However, in the general formula (C2), R ¹⁴ , R ¹⁵ , and R ¹⁶ are Independently a hydrogen atom or an organic group having 1 to 30 carbon atoms (however, at least one is an organic group.), Z is an isocyanate group and / or a hydrolyzable group, and e, g, and h are independently 0, 1, or 2 And 0 ≦ e +
g + h ≦ 3. 12. The base material according to claim 7, wherein the compound (C) is tetraisocyanate silane and / or tetraalkoxy silane. 13. The base material according to claim 7, wherein the treating agent containing the compound (C) contains a metal and / or a metal oxide. 14. A method for producing a substrate having at least two surface-treated layers, which is obtained by treating the surface of a substrate with a treatment agent containing a compound (C) which forms a heat-resistant polymer thin film. The heat-resistant polymer thin film layer is formed by heating the thin film as needed, and then the surface of the heat-resistant polymer thin film layer is removed.
5. A method for producing a base material, which comprises treating with the surface treatment agent according to any one of 5 to 5. 15. A method for producing a base material having at least two surface treatment layers, wherein the surface of the base material is treated with a treatment agent containing a compound (C) forming a heat resistant polymer thin film and polymer fine particles. Then, the resulting thin film is heated to thermally decompose the polymer fine particles to form a heat-resistant polymer thin film layer, and thereafter,
A method for producing a substrate, wherein the surface of the heat-resistant polymer thin film layer is treated with the surface treatment agent according to any one of claims 1 to 5.