JPH10180937A - Surface-treated base material and manufacture of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve water repellent property and contamination preventing property by a method wherein outermost layers of surface-treated layers of a base material having two layers or more of surface-treated layers are obtained by treating by a surface treating agent containing a specified compound while lower layers of the outermost layers are obtained by treating with a surface treating agent containing a specified compound and Si(NCO)4 . SOLUTION: In a base material, applied for the exterior member of tram car, motorcar or the like such as the external plate, window glass and the like, and an interior member for the surface member of dash board and the like, and having two layers or more of surface-treated layers, the outermost layer of the surface treated layers or a first layer is formed by treating it through a surface treating agent containing the essential constituents of compound B shown by a formula (R<3> )c (R<4> )d Si(NCO)4-c-d . On the other hand, the lower layer of the outermost layer or a second layer is formed by treating through surface treating agent, containing the essential constituents of a compound A, shown by a formula (R<1> )a (R<2> )b Si(Z)4-a-b and Si(NCO)4 . In the formulas, R<1> , R<3> are organic groups, R<2> , R<4> are hydrogen atoms or organic groups, Z is an isocyanate group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated substrate having excellent water repellency and antifouling property and a method for producing the same.

[0002]

2. Description of the Related Art Substrates made of various materials and various substrates having a surface treatment layer applied to the substrate are used in various fields, and adsorption of dust and oil stains on the substrate surface, or The adverse effects of water are a problem.

[0003] For example, the outer panels, windowpanes, mirrors, outer layer members such as display device surface materials, inner layer members such as instrument panel surface materials, and the surfaces of other articles in transportation equipment such as trains, automobiles, ships, and aircrafts are always present. Preferably clean, on the surface,
When raindrops, dust, dirt, and the like adhere, and when moisture condenses due to the influence of humidity and temperature in the atmosphere, there is a problem in that the appearance is impaired. In addition, if the surface is in direct contact with or in direct contact with human eyes, discomfort and hygiene problems occur.

[0004] In addition, dirt on transportation equipment articles significantly reduces their original functions. In particular, articles for transportation equipment that require transparency and transparency (for example,
In the case of a window glass, a mirror, etc., a decrease in transparency and transparency means that the intended purpose of the article cannot be achieved, which may cause a serious accident.

[0005] Means for removing such dust, oil stains, and water (eg, wiping, removal with a wiper)
May cause fine scratches on the surface. Foreign particles associated with dust, oil stains, water and the like may further increase the surface damage.

Further, it is well known that when moisture adheres to the glass surface, the glass component is eluted in the moisture and the surface is eroded (a phenomenon called so-called burning). If strong friction is applied to remove this burn, fine irregularities are likely to occur. The see-through part made of severely burned glass or glass with fine irregularities on its surface has its original function deteriorated, and its surface is strongly scattered by light, causing only inconvenience in securing the visual field. But it is also a problem in terms of safety.

[0007] Dust, dirt, and water have a harmful effect on the surface of transportation equipment articles, and promote damage, contamination, coloring, corrosion, etc., and electrical, mechanical, and optical properties of transportation equipment articles. Etc. may be induced. This type of adverse effect is not limited to articles for transportation equipment, but has been a problem in various fields such as articles for construction and construction, articles for electric and electronic equipment, and the like.

For this reason, there is a strong technique for imparting a property of preventing the adhesion of dust, dirt, and water droplets, or a property of facilitating the removal when these are adhered (hereinafter simply referred to as antifouling property) to the substrate surface. It has been demanded.

Hitherto, as a method for imparting antifouling properties, a method has been proposed in which a surface treating agent such as a silicone oil comprising silicone wax or organopolysiloxane or a surfactant is directly applied to a substrate.

[0010] However, the conventional surface treating agent has a drawback that the treating agent itself has low adhesion to the base material, cannot satisfy the long-term durability of the antifouling property, and its application range is limited. .

Furthermore, 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 that have already been used, articles whose performance has been reduced after treatment, and the like. However, if it is intended to apply to all of these articles, it is necessary to impart antifouling properties only by directly treating each part at room temperature. For example, when treating a windshield for a car that is already on the market, it is impossible to replace the windshield of each car and heat-treat it for economic reasons. Further, it is practically impossible to fire the entire automobile after the application. Therefore, there is a problem that it is difficult to cope with the conventional treatment agent and the cost is too high.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a substrate having extremely excellent water repellency and antifouling property and a method for producing the same.

[0013]

According to the present invention, there is provided a substrate having two or more surface treatment layers, wherein the first layer which is the outermost layer of the surface treatment layer is a compound represented by the general formula (B): Surface treatment agent containing B as an essential component (hereinafter referred to as treatment agent B)
And a second layer, which is a lower layer in contact with the outermost layer, is formed of a compound A represented by the general formula (A) and Si (N
The present invention provides a surface-treated substrate characterized by being a layer obtained by treating with a surface treating agent (hereinafter, referred to as treating agent A) containing (CO) ₄ as an essential component, and a method for producing the same.

[0014]

(R ¹ ) _a (R ² ) _b Si (Z) _4-ab (A), (R ³ ) _c (R ⁴ ) _d Si (NCO) _4-cd (B) ).

Wherein R ¹ is an organic group, R ² is a hydrogen atom or an organic group, a is 1, 2 or 3,
b is 0, 1 or 2, and 1 ≦ a + b ≦ 3, and Z is an isocyanate group or a hydrolyzable group.
R ³ is an organic group, R ⁴ is a hydrogen atom or an organic group, c is 1, 2 or 3, d is 0, 1 or 2, and 1 ≦ c + d ≦ 3 .

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound A, when a is 2 or more, R ¹ may be the same or different. When b is 2, R ² may be the same or different.
When 4-ab is 2 or more, Z may be only an isocyanate group or only a hydrolyzable group, or an isocyanate group and a hydrolyzable group may coexist.
In the case of more than one, those hydrolyzable groups may be the same or different from each other.

The organic group includes a halogen atom, a functional group,
It may be an organic group containing 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 organic group preferably has 1 to 30 carbon atoms.

As the hydrocarbon group, an aliphatic hydrocarbon group,
Any of an aromatic hydrocarbon group may be used, and an aliphatic hydrocarbon group is preferable. As the aliphatic hydrocarbon group, an alkyl group,
Alkenyl groups and cycloalkyl groups are preferred, and alkyl groups are particularly preferred. Specifically, a methyl group, an ethyl group,
Examples include a propyl group and a butyl group. As the aromatic hydrocarbon group, an aryl group is preferable.

As the halogen atom of the halogenated organic group, a chlorine atom, a fluorine atom and a bromine atom are preferred, a chlorine atom and a fluorine atom are more preferred, and a fluorine atom is particularly preferred.

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.

As the halogenated organic group, a polyfluoro organic group in which two or more hydrogen atoms of the organic group are substituted with fluorine atoms is preferable. As the polyfluoro organic group, a polyfluoro hydrocarbon group is preferable, and in particular, a polyfluoro hydrocarbon group in which two or more hydrogen atoms of the above-described hydrocarbon group are substituted with fluorine atoms is preferable.

As the polyfluorohydrocarbon group, a polyfluoroalkyl group (hereinafter, the polyfluoroalkyl group is referred to as an ^Rf group) is particularly preferable. The R ^f group means a group in which two or more hydrogen atoms of an alkyl group have been substituted with fluorine atoms.

The ^Rf group preferably has 3 to 18 carbon atoms. R
^{The f} group may be linear or branched. The proportion of fluorine atoms in the R ^f group, (the number of fluorine atoms in the R ^f group) /
(The number of hydrogen atoms in the alkyl group having the same carbon number corresponding to the R ^f group) is preferably 60% or more, particularly preferably 80% or more.

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

The R ^f group is preferably a perfluoroalkyl group in which all of the hydrogen atoms in the above R ^f group have been substituted with fluorine atoms, a group having a perfluoroalkyl moiety, or a group having a perfluoroalkylene moiety. The number of carbon atoms of the perfluoroalkyl group or the perfluoroalkyl moiety is preferably 3 to 21, and the number of carbon atoms of the perfluoroalkylene moiety is preferably 2 to 18.

Particularly, the R ^f group is preferably a group having a structure in which the above-mentioned perfluoroalkyl moiety and alkylene group are linked, and particularly, C _m F _{2m + 1} (CH ₂ ) _n- (m is 3 to 21)
Is preferably an integer, n is preferably an integer of 1 to 6, and n is particularly preferably 2. The R ^f group in the case of formula (I) is preferred.

Z in compound A represents an isocyanate group or a hydrolyzable group. Although there is an idea that the isocyanate group is one kind of hydrolyzable group, in the present invention, it is assumed that the isocyanate group and the hydrolyzable group are different groups. The isocyanate group and the hydrolyzable group are very important structural units for enhancing the adhesion to various substrates when the compound A is treated on the substrate.
Here, “adhesion” means a state of chemical and physical bonding between the compound A and the substrate.

Examples of the hydrolyzable group include an alkoxy group, a halogen (chlorine, bromine, iodine) atom, an acyloxy group,
Examples thereof include an alkoxy-substituted alkoxy group, an aminoxy group, an amide group, and a ketoxime group, and an alkoxy group and a halogen atom are preferred. The number of carbon atoms of the hydrolyzable group is preferably 8 or less, particularly preferably 4 or less. Most preferred is an alkoxy group having 1 to 4 carbon atoms, for example, a methoxy group,
Ethoxy, n-propoxy, isopropoxy, n
-Butoxy group and the like.

Z in compound A is not particularly limited and may be appropriately selected depending on the purpose of use. When there are a plurality of Z's, they may be the same or different, and the same case is preferable from the viewpoint of ease of synthesis.

When Z is different, a hydrolyzable group and an isocyanate group may coexist in a molecule, an isocyanate group and a chlorine atom may coexist, or a different hydrolyzable group may coexist in a molecule. Good. However, in consideration of the reactivity of the compound A, it is preferable that one or more of Z in the compound A is an isocyanate group, particularly from the viewpoints of adhesion to a substrate, work stability during treatment, and the like. , Z are preferably isocyanate groups.

In the following, one compound is present in the compound A molecule.
Compound A having a structure in which two or more isocyanate groups are present and the isocyanate group is directly bonded to a silicon atom,
Described as isocyanate A.

In isocyanate A, since the reactivity of the isocyanate group is extremely high, it is considered that most of the isocyanate group is bonded to the surface of the base material by a chemical reaction when treated at normal temperature. That is, it is considered that the isocyanate group is changed in the bonding state. For example, the isocyanate groups are considered to have reacted with the silanol groups on the glass surface.

In the compound A, it is preferable that the number of isocyanate groups and / or hydrolyzable groups directly bonded to one silicon atom is large from the viewpoint of adhesion to a substrate.
Particularly, the case where the number of isocyanate groups is large is preferable. It is desirable that the number of Z is two or more.

Specific examples of compound A include (A-1) to (A-3)
Although shown in 5), it is not limited to them. In the formula, Z represents an isocyanate group and / or a hydrolyzable group, R ′ represents an organic group, and R ^f represents an R ^f group. (A-17),
M in (A-18), (A-34) and (A-35)
Is an integer of 1 to 10.

As the compound A, one or more of the above compounds can be used. The compound A may be a compound containing ^the R ^f group may be used two or more compounds A with different number of carbon atoms in ^the R ^f group.

[0036]

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[0037]

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Si (NCO) ₄ has _four functional groups,
Since it is much more reactive at room temperature than compound A,
Adhesion with the substrate can be dramatically improved. Si (NCO) ₄
Is considered to react with Si (NCO) _{4 and} also with compound A, so that the cross-linked structure of the resulting film is improved, leading to higher durability of the film. Since treating agent A contains compound A and Si (NCO) ₄ , Si (NCO) ₄
In comparison with the case of only A, the durability (particularly, salt water resistance) is excellent.

In treating agent A, compound A (Si
O) The weight ratio to ₄ is not particularly limited, and is preferably 9
5/5 to 40/60. Compound A Si (NCO)
_If the weight ratio to ₄ is greater than 95/5, Si (NC
O) The addition effect of ₄ is hardly exhibited, and the weight ratio is 40 /
If it is less than 60, the durability (especially salt water resistance) and workability of the membrane will decrease.

The treating agent A is composed of the compound A and Si (NC
Although it may be composed of only O) _4, it is usually preferable to include an organic solvent together with Compound A and Si (NCO) ₄ .

The organic solvent is not particularly limited, and is preferably an organic solvent capable of dissolving or uniformly dispersing Compound A and Si (NCO) ₄ , and particularly, halogenated (fluorine, chlorine, bromine) hydrocarbons and aliphatic hydrocarbons are preferred. The solvent may be selected from various solvents such as hydrogens, aromatic hydrocarbons, esters, ketones, and ethers in consideration of workability, economy, safety, and the like. One or more organic solvents can be used.
Specifically, the following solvents can be exemplified, but the solvent is not limited thereto.

Hexane, octane, toluene, xylene, ligroin, methylene chloride, chloroform. Various fluorocarbons (225 ca (1,1,1,2,2-pentafluoro-3,3-dichloropropane), 225 cb (1,
1,2,2,3-pentafluoro-1,3-dichloropropane), 123, 124, 125, 134a, 141
b, 142b, 152a, etc.).

Benzotrifluoride, 1,3-bis (trifluoromethyl) benzene, perfluoro (tri-n
-Butylamine), perfluoro (tri-n-pentylamine), perfluoroalkanes, perfluoro (2
-N-butyltetrahydrofuran) (see Chemical formula 6), perfluoro (2-n-propyltetrahydrofuran) (see Chemical formula 7), perfluorotoluene, perfluorobenzene, perfluoroxylene, perfluoronaphthalene,
Perfluoroanthracene.

Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexanone,
Acetylacetone, dibutyl ether, 1,4-dioxane, dihexyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethyl acetate, butyl acetate, butyl propionate, ethyl butyrate, butyl butyrate, acetoacetic acid ethyl.

Ethylene glycol monomethyl ether acetate [CH ₃ COOCH ₂ CH ₂ OCH ₃ ], ethylene glycol monoethyl ether acetate [CH ₃ COOCH _2]
CH ₂ OC ₂ H ₅ ], diethylene glycol monoethyl ether acetate [CH ₃ COOCH ₂ CH ₂ OCH ₂ CH]
₂ OC ₂ H ₅ ], diethylene glycol monobutyl ether acetate [CH ₃ COOCH ₂ CH ₂ OCH ₂ CH ₂ O]
C ₄ H ₉ ], glycol diacetate [CH ₃ COOCH ₂ C]
H ₂ OCOCH _3].

[0046]

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[0047]

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In particular, acetates, butyrate esters, ethers, and halogenated (especially fluorinated) hydrocarbons are preferred from the viewpoints of stability, safety, workability, economy and the like of the liquid.

When the compound A has an isocyanate group, an organic solvent having a reactive hydrogen atom is not desirable because it reacts with the isocyanate group of the compound A, but a small amount of a solvent such as alcohol is added for the purpose of improving wettability. You may.

The amount of the organic solvent is preferably 0.1 to 100 parts by weight of the organic solvent for reasons such as film formability (workability), stability, film thickness, and economy. ~ 3
An amount of about 0 parts by weight is preferable.

The treating agent A may contain other compounds and additives depending on the purpose. Other additives may be selected in consideration of reactivity and compatibility with each component, and ultrafine particles of various metal oxides, various resins, and the like can also be added. If coloring is required, dyes, pigments and the like can be added. The amount of these additives is preferably 0.1 to 20 parts by weight based on 100 parts by weight of compound A. If the amount of the additive is excessive, the antifouling property, abrasion resistance and the like of the treating agent A decrease, which is not desirable.

For example, if conductivity is required,
Materials that provide resistance according to the purpose (tin oxide, ITO
(In ₂ O ₃ —SnO ₂ ), zinc oxide, etc.) may be added. The amounts of these additives may be determined according to the desired resistance value and material.

In treating the treating agent A, a pretreatment according to the purpose may be performed. For example, pretreatment such as polishing treatment with cerium oxide or the like, sand blast treatment, acid treatment with hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, etc., alkali treatment with sodium hydroxide, potassium hydroxide aqueous solution or the like, or discharge treatment with plasma irradiation or the like. May go.
Further, the processing may be performed without performing the preprocessing.

The method for treating the treating agent A is not particularly limited. In general, various known treatment methods can be applied. Application methods include brushing, flow coating, spin coating, dip coating,
Various methods such as spray coating are exemplified. Furthermore, a film is formed by drying in air or a nitrogen atmosphere.

All of the above treatments can be performed at room temperature.
20-30 ° C is preferred. The drying time is 10 minutes to 5 minutes.
About 20 hours, preferably 20 minutes to 2 hours. Further, heating may be performed for the purpose of increasing the drying speed. In the case of heating, a temperature and a time at which the heat resistance of the substrate is maintained may be set. Further, it is also preferable to leave and 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 A is appropriately controlled by the solid concentration in the surface treating agent, application conditions, heating conditions and the like, and is not particularly limited. Normally, in order to exhibit antifouling properties, the film thickness of the coating should theoretically be at least a monolayer, and is preferably 2 μm or less from an economic viewpoint.

In the present invention, a surface treating agent (treating agent B) containing the compound B represented by the general formula (B) as an essential component is treated on the film obtained by the treating agent A to form an outermost layer. To improve durability performance. In compound B, when c is 2 or more, R ³ may be the same or different. When d is 2, R ⁴ may be the same or different.

As the organic group, a halogen atom, a functional group,
It may be an organic group containing a linking group or the like. As the organic group, a hydrocarbon group or a halogenated organic group is preferable.
The organic group preferably has 1 to 30 carbon atoms.

As the hydrocarbon group, an aliphatic hydrocarbon group,
Any of an aromatic hydrocarbon group may be used, and an aliphatic hydrocarbon group is preferable. As the aliphatic hydrocarbon group, an alkyl group,
Alkenyl groups and cycloalkyl groups are preferred, and alkyl groups are particularly preferred. Specifically, a methyl group, an ethyl group,
Examples include a propyl group and a butyl group. As the aromatic hydrocarbon group, an aryl group is preferable.

As the halogen atom of the halogenated organic group, a chlorine atom, a fluorine atom and a bromine atom are preferred, a chlorine atom and a fluorine atom are more preferred, and a fluorine atom is particularly preferred.

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 have been substituted with fluorine atoms. As the polyfluoro organic group, a polyfluoro hydrocarbon group is preferable, and in particular, a polyfluoro hydrocarbon group in which two or more hydrogen atoms of the above-described hydrocarbon group are substituted with fluorine atoms is preferable. As the polyfluorohydrocarbon group, an R ^f group is particularly preferable.

The R ^f group preferably has 3 to 18 carbon atoms. R
^{The f} group may be linear or branched. The proportion of fluorine atoms in the R ^f group, (the number of fluorine atoms in the R ^f group) /
(The number of hydrogen atoms in the alkyl group having the same carbon number corresponding to the R ^f group) is preferably 60% or more, and particularly preferably 80% or more.

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

The R ^f group is preferably a perfluoroalkyl group in which all of the hydrogen atoms in the above R ^f group have been substituted with fluorine atoms, a group having a perfluoroalkyl moiety, or a group having a perfluoroalkylene moiety. The number of carbon atoms of the perfluoroalkyl group or the perfluoroalkyl moiety is preferably 3 to 21, and the number of carbon atoms of the perfluoroalkylene moiety is preferably 2 to 18.

Particularly, the R ^f group is preferably a group having a structure in which the above-mentioned perfluoroalkyl moiety and alkylene group are linked, and particularly, C _m F _{2m + 1} (CH ₂ ) _n- (m is 3 to 21)
Is preferably an integer of 1 to 6, and n is 2
Is particularly preferred. The R ^f group in the case of formula (I) is preferred.

The isocyanate group in the compound B is a very important structural unit for enhancing the adhesion when the compound B is treated on the surface of the film obtained by the treating agent A. Here, “adhesion” means a state of chemical and physical bonding between the compound B and the surface of the film obtained from the treating agent A.

In the compound B, the reactivity of the isocyanate group is very high, and it is considered that most of the compound B is bound by a chemical reaction when treated at room temperature. That is, it is considered that the isocyanate group is changed in the bonding state. For example, it is considered that the isocyanate group has reacted with the silanol group on the surface obtained from the treating agent A.

In the compound B, the number of isocyanate groups directly bonded to one silicon atom is preferably large from the viewpoint of adhesion to the film obtained from the treating agent A, and the number is preferably 2 or more.

The compound A and Si (NCO) ₄ (mostly Si (NC)
O) ₄ ) Unreacted group portion (Si-NCO group) as it is or reacted with moisture in the air (Si-OH group)
It seems to exist in.

Accordingly, when the surface of the film obtained from the treating agent A is treated with the treating agent B, the Si—NCO group, S
The i-OH group is considered to be the starting point of the reaction, and the film obtained from the compound B and the treating agent A adheres firmly and the effective film thickness of the film increases, so that the durability of the film is dramatically improved. Seem. In addition, favorable results can be obtained also in terms of durability (particularly, salt water resistance).

Compound B is a substance having a low surface free energy. The compound B in a free state, which is only partially present in the film, moves through the surface layer to reduce the frictional resistance on the surface. It is considered that the wear properties are good.

The compound B is usually preferably used by dissolving and dispersing it in an organic solvent from the viewpoint of workability and economy. The organic solvent is not particularly limited, and preferably dissolves or uniformly disperses Compound B, and includes halogenated (fluorine, chlorine, bromine) hydrocarbons, aromatic hydrocarbons, esters, ketones, ethers and the like. Of various solvents are employed.
One or more organic solvents can be used.

In particular, acetates, 225 ca, 2
25 cb, perfluoro (tri-n-butylamine),
Perfluoro (tri-n-pentylamine), perfluoroalkane, perfluorobenzene, perfluoroxylene, perfluoronaphthalene, perfluoroanthracene, perfluorotoluene, perfluoro (2-n
-Butyltetrahydrofuran), perfluoro (2-n
-Propyltetrahydrofuran), benzotrifluoride, 1,3-bis (trifluoromethyl) benzene and the like are preferred.

The organic solvent having a reactive hydrogen atom is not desirable because it reacts with the isocyanate group of the compound B, but may be added in a small amount for the purpose of improving the wettability. As the amount of the organic solvent, the amount of the compound B is 0.1 to 30 parts by weight based on 100 parts by weight of the organic solvent for reasons such as film formability (workability), stability, film thickness, and economy. Is preferred.

The treating agent B may contain other compounds and additives depending on the purpose. As other additives, the above-mentioned additives for compound A and Si (NCO) ₄ can be used similarly.

The method for treating the treatment agent B into a film obtained from the treatment agent A is not particularly limited. In general, various known treatment methods can be applied. Examples of the application method include various methods such as brush coating, flow coating, spin coating, dip coating, and spray coating. Further, a film is formed by drying in air or nitrogen atmosphere.

All of the above treatments can be carried out at normal temperature.
20-30 ° C is preferred. The drying time is about 10 minutes to 5 hours, preferably 20 minutes to 2 hours. Heating may be performed for the purpose of increasing the drying speed. In the case of heating, a temperature and a time at which the heat resistance of the substrate is maintained may be set. Also,
It is also preferable to leave it in a high humidity (for example, 50% or more) environment and dry it.

The thickness of the film formed by treating the substrate with the compound B is appropriately controlled by the solid concentration in the surface treating agent, the application conditions, the heating conditions, and the like, and is not particularly limited. Normally, in order to exhibit antifouling properties, the film thickness of the coating should theoretically be at least a monolayer, and is preferably 2 μm or less from an economic viewpoint. Compound A and Si (NCO) ₄
The total film thickness of the layer formed of the compound B and the layer formed of the compound B is preferably 2 μm or less from an economic viewpoint.

Specific examples of compound B include (A-1)
Examples of the compound represented by (A-35) include compounds in which Z is an isocyanate group. Compound B may be the same or different from Compound A. In addition, as the compound B, one or more kinds can be used. Further, when the compound B is a compound containing ^the R ^f group may be used two or more kinds of compounds having different numbers of carbon atoms in ^the R ^f group.

The substrate of the present invention is not particularly limited.
The present invention can be applied to metals, plastics, ceramics, glass, other inorganic and organic materials, or combinations thereof (composite materials, laminated materials, and the like). 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 painted metal, or the surface of a surface-treated layer of a surface-treated glass (for example,
The surface may be made of a material different from the base material itself, such as a sol-gel film, a sputtered film, a CVD film, or a surface provided with a vapor-deposited film. The shape of the substrate is not particularly limited. For example, it may be a flat surface, or may have any shape according to the purpose, such as having a curvature over the entire surface or a part.

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

The transportation equipment articles include outer panels of transportation equipment such as trains, buses, trucks, automobiles, ships, and aircraft.
It refers to exterior members such as window glass, mirrors and display device surface materials, interior members such as instrument panel surface materials, and other components and components used or used in transportation equipment.

Train bodies, window glasses, pantographs, etc., bodies of cars, buses, trucks, etc., windshields, side glasses, rear glasses, mirrors, bumpers, etc.
A body such as a ship, a window glass, an aircraft body, a window glass, and the like can be exemplified.

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 there is a rearview mirror member for an automobile in which a glass mirror is incorporated as the latter.

In such base materials and articles, water droplets adhering to the surface are repelled by the water droplet removing property. In particular, the water droplets rapidly move on the surface due to the interaction with the received wind pressure during operation, and do not accumulate as water droplets. , Eliminates the adverse effects of moisture. In particular, when used in a transparent field of view such as various window glasses, the scattering of water droplets makes it very easy to secure the field of view, which contributes to the improvement of vehicle safety.

Further, even in an environment where water droplets freeze, they do not freeze, and even if they freeze, thawing is extremely fast. Furthermore, since there is almost no adhesion of water droplets, the number of regular cleaning operations can be reduced, and cleaning is extremely easy, which is very advantageous from the viewpoint of protection of aesthetics.

The article for building / building is an article attached to a building, an article already attached to a building, an article for building which is not attached to a building but used together with it, or furniture. , Furniture, etc.

Various types of roofs, including window glass, roof glass plates and glass roofs, door glass plates and doors into which they are fitted, door partitions, glass plates for greenhouses, greenhouses, and transparent plastic plates are used. Window materials, roof materials, etc.
Examples thereof include 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 solely of the surface-treated substrate, or may incorporate the surface-treated substrate. For example, the former is a window glass plate, and the latter is furniture incorporating a glass mirror.

In such a surface-treated substrate,
Water droplets that have come into contact with the surface are repelled and hardly adhere due to the water droplet removal property. Even if they adhere, the amount of the water droplets is small, and the adhered water droplets can be easily removed. In addition, it does not freeze even in an environment where water droplets freeze, and even if it freezes, thawing is extremely fast. Further, since there is almost no adhesion of water droplets, the number of regular cleaning operations can be reduced, and the cleaning is extremely easy, which is very advantageous from the viewpoint of aesthetic protection.

The treating agent A has an advantage that it exhibits its performance at room temperature. Further, since no special pre-processing or post-processing is required, the processing can be easily performed. Therefore, it is possible to treat not only a new substrate but also a substrate already used for some purpose. In addition, treatment agent A
It can also be used for repairing if the performance of the coating deteriorates for some reason after the treatment.

[0093]

EXAMPLES The present invention will be specifically described with reference to examples, but is not limited thereto. In addition, Examples 1-5 and Examples 11-2
2 corresponds to an example, and examples 6 to 10 correspond to comparative examples.

The methods for evaluating the antifouling property, the antifouling durability and the antifouling property after the salt spray test are as follows.

[Evaluation Method of Antifouling Property] a) The contact angle of water (H ₂ O) was measured. B) The contact angle of hexadecane (C ₁₆ H ₃₄ ) was measured. C) The fingerprint removability was evaluated by the following method. That is, a fingerprint of a hand is adhered to the treated surface, wiped back and forth with a cotton cloth for 20 reciprocations, and then inspected for appearance. A: Completely wipe off oil stains, B: Slightly oil stains remaining, C: Quite oil stains remain The evaluation was based on the following criteria. D) Water droplet persistence was evaluated by the following method. That is, after water was sprayed 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 were visually observed, and A: no water remained on the sample surface, B: The evaluation was based on the criteria that a small amount of water remains on the sample surface, C: considerable water droplets remain on the sample surface, and D: water wets and spreads on the sample surface.

[Evaluation Method of Antifouling Durability] After dipping in boiling water for 6 hours, (c) fingerprint removal property and (d) water droplet remaining property were evaluated.

[Evaluation method of antifouling property after salt spray test]
The antifouling property of the sample glass after performing the salt spray test for 150 hours in accordance with IS Z2371 was evaluated.

The "fingerprint" column and the "waterdrop" column in the table mean the fingerprint removal property and the waterdrop remaining property, respectively.

Example 1 97.0 g of n-butyl acetate and C ₈ F ₁₇ C were placed in a flask in which a stir bar and a thermometer were set.
2.4 g of ₂ H ₄ Si (NCO) ₃ , Si (NCO) ₄
0.6 g was added in this order. While maintaining the solution temperature at 25 ° C., stirring was continued for 24 hours to obtain a treating agent A.

On the other hand, 97.0 g of n-butyl acetate, C ₈ F ₁₇ C _{2 were} placed in a flask in which a stir bar and a thermometer were set.
3.0 g of H ₄ Si (NCO) ₃ was added in this order. Stirring was continued for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent B-1.

1 cc of the treating agent A-1 was dropped on a glass plate (10 cm × 10 cm × 2 mm thick) which had been polished with cerium oxide in advance and washed with a JK wiper (manufactured by Jujo Kimberly) in the manner of waxing an automobile. I spread it. At this time, the coating workability was evaluated based on the following criteria: ○: Easy spreading without any trouble, Δ: A little effort in spreading, ×: Considerable labor in spreading. Table 1 shows the evaluation of the coating workability.

Next, the plate was allowed to stand for 1 hour in an environment of 25 ° C. and 50% humidity.
c, and was spread in the same manner as described above using a JK wiper. Then, it was left for one day and night to prepare a sample glass. Table 2 shows the results of evaluating the antifouling property, antifouling durability and antifouling property after the salt spray test of the obtained sample glass. In Table 2, “good” in the “appearance” column means “good”.

Example 2 C ₈ F ₁₇ C ₂ H ₄ Si (NCO)
₃ Instead of 2.4 g, Si (NCO) ₄ 0.6 g, C ₈
1.5 g of F ₁₇ C ₂ H ₄ Si (NCO) ₃ , Si (NC
O) Treatment agent A in the same manner as in Example 1 except that 1.5 g of ₄ ) was used.
-2 was obtained. Hereinafter, instead of treating agent A-1, treating agent A-
A sample glass was prepared in the same manner as in Example 1 except that Sample No. 2 was used, and the coating workability, antifouling property, antifouling durability and antifouling property after a salt water spray test were evaluated. Table 2 shows the results.

[Examples 3 to 5] Table 1 in place of treating agent A-2
Sample glasses were prepared in the same manner as in Example 2 except that the treating agents shown in the "Lower Layer" column were used, and the same evaluations were made. Table 2 shows the results.

[Example 6] A lower layer treating agent was applied in the same manner as in Example 3, and then left for a day to prepare a sample glass. The same evaluation as in Example 1 was performed. Table 2 shows the results.

Example 7 The same evaluation as in Example 1 was performed without any treatment on the glass plate of Example 1. Table 2 shows the results.

[Examples 8 to 9] Sample glasses were prepared in the same manner as in Example 6, except that the treating agents shown in the “lower layer” column of Table 1 were used instead of the treating agents in the lower layer of Example 6. Was evaluated. Table 2 shows the results.

[Example 10] The treating agent shown in the "lower layer" column of Table 1 was used instead of treating agent A-1, and the treating agent shown in the "upper layer" column of Table 1 was used instead of treating agent B-1. Other than the above, a sample glass was prepared in the same manner as in Example 1, and the same evaluation was performed.
Table 2 shows the results.

Example 11 29.1 g of n-butyl acetate and C ₈ F _{17 were} placed in a flask equipped with a stir bar and a thermometer.
2.4 g of C ₂ H ₄ Si (NCO) ₃ , Si (NCO) ₄
0.6 g and 67.9 g of 1,3-bis (trifluoromethyl) benzene were added in this order. While maintaining the solution temperature at 25 ° C., stirring was continued for one day and night to treat the treating agent A-3.
I got

On the other hand, 97.0 g of N (n-C ₄ F ₉ ) ₃ and C ₈ F were placed in a flask in which a stirrer and a thermometer were set.
3.0 g of ₁₇ C ₂ H ₄ Si (NCO) ₃ were added in this order. Stirring was continued for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent B-2.

Hereinafter, instead of the treating agent A-1, the treating agent A-
Sample glass was prepared in the same manner as in Example 1 except that the treating agent B-2 was used instead of the treating agent B-1 in Example 3, and the coating workability, antifouling property, antifouling durability and salt spray test were performed. The subsequent antifouling properties were evaluated. Table 2 shows the results.

[Examples 12 to 15] The treating agents shown in the "lower layer" column of Table 1 were used instead of treating agent A-3, and the treating agents shown in the "upper layer" column of Table 1 were used instead of treating agent B-2. Sample glasses were prepared in the same manner as in Example 11 except for using, and the same evaluation was performed. Table 2 shows the results.

Example 16 The sample glass of Example 1 was immersed in the chemicals shown in Table 2 for 24 hours, taken out and washed immediately, and the appearance change, fingerprint removability and water droplet remaining property of this sample were evaluated. Table 3 shows the results.

[Example 17] A load of 1 was applied to the sample glass of Example 1.
20,000 reciprocal abrasions were carried out with a flannel cloth. Table 4 shows the evaluation results of the antifouling property after the abrasion test.

[Example 18] Ultraviolet irradiation was performed for 8 hours (70 hours).
C), and the wet exposure was performed for 4 hours (50 ° C.) as one cycle.
0 cycles were performed. Table 4 shows the evaluation results of the antifouling property after the weather resistance test.

Example 19 After the surface of a front laminated glass for an automobile was treated by the method of Example 1, the laminated glass was mounted on an automobile. 4 hours during the day, 2 nights
A time running test was performed for one month, and the state of dirt and dust on the front surface and the state of water droplets on rainy days were visually observed every day.

[0117] As a result, no generation of dirt, dust and adhesion of water droplets due to the adhesion of water droplets was observed at all, and even in the rare cases where such generation was recognized, they were easily removed by gently wiping with tissue paper.

Further, in rainy weather, water droplets on the surface were repelled and moved promptly due to interaction with wind pressure during traveling, so that the field of view was secured without using a wiper.
Further, in a running test (0 to -5 ° C) in an environment (0 to -5 ° C) where water droplets adhering to the untreated front laminated glass freeze or the water in the air condenses and freezes on the windshield. No freeze was seen.

Next, in a severer low temperature environment (−10 to
At −15 ° C.), icing on the windshield was observed, but the thawing was fast and it was confirmed that the glass had significantly better performance than the untreated windshield.

[Example 20] A running test was performed by changing the front laminated glass of Example 19 to a side glass, a rear glass, and a side mirror. The same effect as in Example 19 was confirmed.

[Example 21] A front laminated glass of an automobile which has been used for three years has been polished with cerium oxide, washed with water and dried. 10 cc of the solution of the treating agent A-1 was dropped on the washed front laminated glass, applied with a JK wiper in the manner of car waxing, and left for 1 hour. At this time, the temperature was 19 ° C. and the humidity was 46%. Further, 10 cc of the treating agent B-1 was dropped on the treated surface, spread in the same manner as in the case of car waxing with a JK wiper, and allowed to stand for one day. When a test similar to that of Example 19 was performed using this automobile, the same effect as that of Example 19 was confirmed.

Example 22 A coating was formed on the surface of a building window glass by the method of Example 1. The windowpane thus obtained was installed in the house. The state of adhesion of dirt and dust on the surface of the window glass and the state of adhesion of water droplets in rainy weather were visually observed.

As a result, no generation of dirt, dust and adhesion of water droplets due to the adhesion of water droplets was observed at all, and even in the rare cases where such generation was observed, they were easily removed by gently wiping with tissue paper. Also, in rainy weather, water droplets on the surface were repelled and fell down, and especially on a windy day, they quickly moved due to the interaction with wind pressure to secure a visual field.
Further, in a test in an environment (0 to -5 ° C.) where water droplets adhering to an untreated window glass freeze or water in the air condenses and freezes on the window glass, freezing on the window glass occurs. Was not seen at all.

Next, in a severer low temperature environment (−10 to
At −15 ° C.), icing on the window glass was also observed, but the thawing was fast and it was confirmed that the glass had remarkably superior performance as compared with the untreated window glass.

[0125]

[Table 1]

[0126]

[Table 2]

[0127]

[Table 3]

[0128]

[Table 4]

[0129]

【The invention's effect】

(1) According to the method of the present invention, treatment at normal temperature is possible, and excellent antifouling property can be imparted to a substrate. Therefore, not only can a newly manufactured article be processed, but also an already used article can be processed. Further, since heat treatment is not required, necessary parts can be appropriately processed without breaking the shape of the article.

(2) 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, and continuous treatment can be performed, which is economically advantageous.

(3) The substrate of the present invention or an article provided with the same has excellent antifouling properties, and adheres to dust, dirt, water droplets,
Or, no scale is generated thereby, and even in the rare case where they are generated, they can be easily removed and the adverse effects induced by water can be blocked, thereby simplifying the cleaning.

(4) The base material of the present invention or an article provided with the base material has excellent antifouling properties, salt water resistance,
Since it has chemical resistance, abrasion resistance, and weather resistance, the antifouling property is excellent and the antifouling property is maintained semipermanently.

The effects described above cannot be expected by the conventional method, and it is expected that the range of application can be extended to fields that have been unusable up to now.

Claims (8)

[Claims] 1. A substrate having two or more surface treatment layers, wherein the first layer, which is the outermost layer of the surface treatment layer, contains the compound B represented by the general formula (B) as an essential component. The second layer, which is a layer obtained by treating with a treating agent and which is a lower layer in contact with the outermost layer, comprises a compound A represented by the general formula (A) and Si (N
A surface-treated base material, which is a layer obtained by treating with a surface treatment agent containing (CO) ₄ as an essential component. (R ¹ ) _a (R ² ) _b Si (Z) _4-ab (A) (R ³ ) _c (R ⁴ ) _d Si (NCO) _4-cd (B) Provided that R ¹ is an organic group, R ² is a hydrogen atom or an organic group, a is 1, 2 or 3, b is 0, 1 or 2, and 1 ≦ a + b ≦ 3 And Z are isocyanate groups or hydrolyzable groups. R ³ is an organic group; R ⁴ is a hydrogen atom or an organic group;
Is 1, 2 or 3, d is 0, 1 or 2,
In addition, 1 ≦ c + d ≦ 3. 2. The surface-treated substrate according to claim 1, wherein the weight ratio of compound A to Si (NCO) ₄ is 95/5 to 40/60. 3. The surface-treated substrate according to claim 1, wherein one or more of Z is an isocyanate group. 4. The surface-treated substrate according to claim 1, wherein all of Z is an isocyanate group. 5. A method for producing a substrate having two or more surface treatment layers, wherein the substrate surface contains the compound A represented by the general formula (A) and Si (NCO) ₄ as essential components. A method for producing a surface-treated substrate, comprising treating the surface with a surface treating agent containing a compound B represented by the general formula (B) after treating with a surface treating agent. (R ¹ ) _a (R ² ) _b Si (Z) _4-ab (A) (R ³ ) _c (R ⁴ ) _d Si (NCO) _4-cd (B) Provided that R ¹ is an organic group, R ² is a hydrogen atom or an organic group, a is 1, 2 or 3, b is 0, 1 or 2, and 1 ≦ a + b ≦ 3 And Z are isocyanate groups or hydrolyzable groups. R ³ is an organic group; R ⁴ is a hydrogen atom or an organic group;
Is 1, 2 or 3, d is 0, 1 or 2,
In addition, 1 ≦ c + d ≦ 3. 6. The method for producing a surface-treated substrate according to claim 5, wherein the weight ratio of compound A to Si (NCO) ₄ is 95/5 to 40/60. 7. The method according to claim 5, wherein at least one of Z is an isocyanate group. 8. The method for producing a surface-treated substrate according to claim 5, wherein all of Z are isocyanate groups.