JPH04342444A - Article having treated surface for teansportation equipment - Google Patents

Abstract

PURPOSE:To provide a base material or an article, excellent in water repellency and used for transportation, equipment. CONSTITUTION:A base material is obtained by forming two layers of a lower layer prepared by treating the surface with a hydrolyzable silane compound or its partial hydrolyzate and further treating the surface of the resultant lower layer with a fluorinecontaining hydrolyzable silane compound or its partial hydrolyzate or an article, composed of a base material having the aforementioned surface-treated layers as a constituent element, thus the base material useful for transportation equipment is provided. Glass requiring excellent see- through visibility is suitable as the base material. Window glass or mirrors are exemplified as the article for the transportation equipment. Since the aforementioned article has excellent water repellency and abrasion, chemical and weather resistances together, its effects are semipermanently sustained. Therefore, the above-mentioned article is excellent as an article for the transportation equipment under severe use environments.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article for transportation equipment that can maintain a water-repellent surface for a long period of time, on which water droplets are less likely to adhere or the adhered water droplets can be easily removed.

0002

[Prior Art] Exterior parts such as outer panels, window glasses, mirrors, display device surface materials, interior materials such as instrument panel surface materials, and other surfaces of transportation equipment such as trains, automobiles, ships, and aircraft are constantly It is preferable that it is clean. When raindrops, dust, dirt, etc. adhere to the surface of an article for transportation equipment, or when moisture condenses due to the influence of atmospheric temperature or humidity, the appearance of the article is impaired. Discomfort and hygiene issues can also arise if it is a surface that is directly visible or comes into contact with people.

[0003]Furthermore, the original function of the surface of the article for transportation equipment is significantly deteriorated. In particular, if the article for transportation equipment is an article that requires transparency and visibility (e.g. window glass, mirrors, etc.), this type of phenomenon can lead to the article not even being able to achieve its original purpose. It may also cause a serious accident.

[0004]Means for removing water droplets and the like (for example, wiping or using a wiper) sometimes cause minute scratches on the surface. Further, foreign particles accompanying water droplets or the like may make such damage even more severe. Furthermore, it is well known that when moisture adheres to a glass surface, glass components dissolve into the moisture, causing the surface to erode and cause so-called burns. If strong friction is applied to remove this burn, fine irregularities are likely to occur. Transparent viewing areas made of glass that is severely burnt or has minute irregularities on its surface are not safe because their original function is degraded and the surface scatters light severely, making it difficult to maintain a clear field of view. I have a sexual problem.

[0005] In addition, moisture has a harmful effect on the surface of transportation equipment articles, promoting damage, contamination, coloring, corrosion, etc., and also impairs the electrical properties, mechanical properties, etc. of transportation equipment articles. It may also induce changes in optical properties, etc.

[0006] Under these circumstances, it is necessary to impart water-repellent properties (hereinafter referred to as water repellency) to the surface of articles for transportation equipment, and to maintain the surface for a long period of time to which less water droplets adhere or to which the attached water droplets can be easily removed. There is a strong need to be able to learn. In order to make the surface water repellent, surface treatment agents have been proposed in which, for example, silicone waxes, silicone oils made of organopolysiloxane, surfactants, etc. are directly applied.

However, many of these require pretreatment for coating, and there are problems in that coating unevenness tends to occur during coating. Furthermore, due to the low adhesion of the treatment agent itself to the substrate, long-term sustainability of water repellency cannot be achieved, and the range of application of the treatment agent is limited.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems. That is, in the process of researching and considering a treatment agent that can eliminate the drawbacks of conventional proposals, the present inventor developed a treatment that can be applied to many types of base materials and that exhibits excellent water repellency. I found a drug. Furthermore, it has been confirmed that various substrates treated with the treatment agent are extremely suitable as water-repellent substrates, particularly as articles for transportation equipment, and the present invention has been completed. Therefore, an object of the present invention is to provide an article for transportation equipment that has water repellency and is excellent in abrasion resistance, chemical resistance, and weather resistance, and whose effects last semi-permanently.

[0009]

[Means for Solving the Problems] The present invention is the following invention that achieves the above objects.

[0010] An article for transportation equipment consisting of a base material having at least two surface treatment layers, or having the base material as a component, wherein the first layer which is the outermost layer of the surface treatment layers has two or more surface treatment layers. A layer obtained by treatment with a fluorine-containing organosilane compound (I) having an organic group having a fluorine atom and a hydrolyzable group or a partial hydrolysis product thereof,
The second layer, which is the lower layer in contact with the outermost layer, is a hydrolyzable silane compound (II) other than the above-mentioned fluorine-containing organosilane compound.
Or an article for transportation equipment, which is a layer obtained by treatment with a partial hydrolysis product thereof.

In the present invention, the fluorine-containing organosilane compound (I) has a structure in which at least one organic group having two or more fluorine atoms and at least one hydrolyzable group are bonded to the same or different silicon atoms. means a compound that has The organic group and the silicon atom are bonded through a carbon-silicon bond, and the hydrolyzable group is also bonded directly to the silicon atom. The organic group and the silicon atom may be bonded to different silicon atoms in the same molecule (in this case, the same molecule has two or more silicon atoms), or may be bonded to the same silicon atom. Further, an organic group other than an organic group having two or more fluorine atoms may be bonded to the silicon atom. The organic group having two or more fluorine atoms is usually a monovalent organic group, but may be a divalent or more polyvalent organic group that bonds between two silicon atoms.

The hydrolyzable silane compound (II) means a compound having a structure in which at least one hydrolyzable group is bonded to a silicon atom. This compound may be a compound in which only a hydrolyzable group is bonded to a silicon atom (for example, a tetraalkoxysilane), or may be a compound in which at least one organic group is bonded to a silicon atom. . However, the organic group in this case is not an organic group having two or more fluorine atoms.

The hydrolyzable group in these compounds is a group bonded to a silicon atom that reacts with water and is eliminated to produce a hydroxyl group (silanol group) bonded to the silicon atom. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, acyloxy groups, alkoxy-substituted alkoxy groups, aminoxy groups, amide groups, acid amide groups,
These include ketoximate groups. Preferably, it is a hydrolyzable group bonded to a silicon atom through an oxygen atom, such as an alkoxy group or a substituted alkoxy group, acyl. The number of carbon atoms in these hydrolyzable groups is preferably 8 or less, particularly 4 or less. A preferred hydrolyzable group is an alkoxy group having 4 or less carbon atoms (hereinafter also referred to as lower alkoxy group).

[0014] The partial hydrolysis products of the fluorine-containing organosilane compound (I) and the hydrolysable silane compound (II) are silanol groups produced by partially hydrolyzing these silane compounds in water or an acidic aqueous solution. or a compound in which two or more molecules are condensed by a reaction of its silanol groups. As the acid, for example, hydrochloric acid, acetic acid, phosphoric acid, nitric acid, sulfuric acid, sulfonic acid, etc. can be used.

[0015] The above-mentioned surface treated with a silane compound having a hydrolyzable group or its partial hydrolysis product refers to a surface to which a silane compound is chemically or physically bonded. Since the hydrolyzable group is decomposed by moisture to form a silanol group, it is thought that these silane compounds are bonded to the surface mainly through a chemical reaction of the silanol group. That is, for example, it is thought that this silanol group undergoes a dehydration condensation reaction with the silanol group on the glass surface. It is also thought that the first layer also bonds with the silanol groups on the surface of the second layer.

In the present invention, articles for transportation equipment include exterior members such as outer panels, window glasses, mirrors, display device surface materials, etc., and interior components such as instrument panel surface materials in transportation equipment such as trains, automobiles, ships, and aircrafts. , parts and components used in or used in other transportation equipment. The article may consist solely of a surface-treated substrate or may incorporate a surface-treated substrate. For example, the former is an automobile window glass, and the latter is an automobile rearview mirror member incorporating a glass mirror.

[0017] The type of substrate for the article for transportation equipment is not particularly limited. For example, metals, plastics, glass, ceramics, other inorganic and organic materials,
Or there are combinations thereof (composite materials, laminated materials, etc.). In addition, the surface of the base material is not only the surface of the base material itself, but also the surface of a material different from that of the base material, such as the surface of a coating such as a painted metal plate or the surface of a surface treatment layer of surface-treated glass. There may be. Moreover, the shape of the base material is not limited to a flat plate, and it goes without saying that it may have any shape depending on the purpose, such as one having curvature on the entire surface or partially.

Particularly suitable substrates in the present invention are substrates made of transparent materials such as glass and transparent plastics, and the articles take advantage of their transparency. Examples include window materials, mirrors, and instrument panel protective covers made of glass or transparent plastic. This is because the see-through visibility is likely to deteriorate due to the adhesion of raindrops, dust, dirt, etc., and there is a high possibility that a serious situation will occur due to problems caused by this. Glass is particularly preferred as the base material.

Surface treatment of the substrate is usually carried out by applying a silane compound or a composition containing the same to the surface and bonding the silane compound to the surface. The composition is preferably a solution containing a solvent. Further components may be present in this solution. Other components include, for example, a binder component and metal oxide fine particles as described below.

[0020] The silane compound comes into contact with the surface of the substrate by application to the surface of the substrate or subsequent volatilization of the solvent and undergoes hydrolysis.
It is thought that a bonding reaction occurs. In this case, drying after coating may be performed at room temperature, heating and drying, or the formed layer may be baked. The temperature of heat drying or firing is preferably 200 °C or less, and the time is 12
0 hours or less is preferable. If heating is performed at too high a temperature or for a long time, the adhesion of the layers (especially in the case of the second layer,
Adhesion of the first layer to the second layer) is adversely affected.

[0021] The thickness of the surface treatment layer produced by this surface treatment is not particularly limited, but it is preferable that at least the first layer is extremely thin. The preferred thickness of the first layer is 20μ or less, particularly 2μ or less. Moreover, the lower limit is the monomolecular layer thickness. Of course, a larger layer thickness can be obtained by blending a larger amount of binder components, metal oxide fine particles, etc. Preferably, the second layer also has a similar thin layer thickness as the first layer. However, the second layer can also be thicker. The layer thickness can be adjusted to a desired thickness by adjusting the concentration of layer-forming components of the composition such as a solution, coating conditions, heating conditions, etc.

Preferred compounds as the fluorine-containing organosilane compound (I) are compounds having 1 to 2 silicon atoms to which a hydrolyzable group is bonded. A preferred fluorine-containing organosilane compound (I) is a compound represented by the following formula (A) or (B). In the following, the compound represented by formula (A) is also referred to as compound (A), and the compound represented by formula (B) is also referred to as compound (B).

(A) X3-a-b(R1)a(R2)bSi-Y
-Si(R3)c(R4)dX3-c-dHowever, X
is a hydrolyzable group, R1, R2, R3, R4 are independently hydrogen or an organic group having 1 to 16 carbon atoms, a and b are independently 0
, 1, 2, and integers satisfying 0≦a+b≦2; c, d are independently 0, 1, 2, and 0≦c+d
an integer satisfying ≦2, and Y represents a divalent organic group, and Y or at least one of R1 to R4 present is an organic group having two or more fluorine atoms.

(B) (Rf)eR5gR6hSiX
4-egh-h However, X is a hydrolyzable group, Rf is 2
An organic group having the above fluorine atom, R5 and R6 are independently hydrogen or an organic group having 1 to 16 carbon atoms, e is 1, 2,
3, g, h are independently 0, 1, 2, 3, and 1
Represents an integer satisfying ≦e+g+h≦3.

Compound (A) is a compound having two silicon atoms to which a hydrolyzable group is bonded, and compound (B) is a compound having one silicon atom to which a hydrolyzable group is bonded. R1 to R6 are preferably organic groups rather than hydrogen atoms. In particular, all R1 to R6 present
is preferably an organic group.

When two or more hydrolyzable groups X are present in the molecule, each hydrolyzable group may be different. Of course,
Compound (A), Compound (B), and Compound (C) described below
The hydrolyzable groups X in may be different from each other. In compound (A) and compound (B), the number of hydrolyzable groups bonded to a silicon atom is preferably two or more per silicon atom. This is because it is thought that the more hydrolyzable groups there are, the stronger the bond to the substrate surface becomes.

Rf is a monovalent organic group having two or more fluorine atoms, and it is a polyfluoroalkyl group, a polyfluorooxaalkyl group, a polyfluorothioxaalkyl group, or a combination of any of these groups and an alkylene group. An organic group (bonded to a silicon atom at the other end of the hydrocarbon group) is preferable, which is bonded to a hydrocarbon group through an ester bond or other connecting bond as described below. A polyfluoroalkyl group, a polyfluorooxaalkyl group, and a polyfluorothioxaalkyl group are those groups in which the end bonded to the silicon atom or the vicinity thereof is an alkylene group (in particular, a dimethylene group), and the other part is perfluoro. It is preferable that

The perfluoro moiety of the monovalent organic group is preferably a perfluoroalkyl group having 3 or more carbon atoms, a perfluorooxaalkyl group, or a perfluorothioxaalkyl group, particularly a perfluoroalkyl group having 3 to 16 carbon atoms. is preferred. When e is 2 to 3, the plurality of Rfs may be different.

R1 to R4 are preferably organic groups, and when Y described later is not a divalent organic group having two or more fluorine atoms, at least one of the organic groups present in R1 to R4 is an organic group having two or more fluorine atoms. It must be a monovalent organic group having a fluorine atom. In this case, the monovalent organic group having two or more fluorine atoms is an organic group equivalent to the above Rf (
Hereinafter, a monovalent organic group having two or more fluorine atoms in compound (A) will also be represented by Rf).

When R1 to R4 are organic groups other than Rf,
The organic group is a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a chloroalkyl group,
Other halogenated hydrocarbon groups other than Rf, hydroxyl groups, epoxy groups, amino groups, mercapto groups, carboxyl groups,
Preferred are (halogenated) hydrocarbon groups having other functional groups, and (halogenated) hydrocarbon groups having an ester bond, ether bond, thioether bond, imino bond, amide bond, or other linking bond in the middle of the carbon chain. . Particularly preferred are hydrocarbon groups and hydrocarbon groups having the above-mentioned functional groups. Preferred hydrocarbon groups include alkyl groups having 1 to 16 carbon atoms and aryl groups. In particular, an alkyl group having 4 or less carbon atoms (hereinafter referred to as a lower alkyl group) is preferred. A particularly preferred lower alkyl group is a methyl group.

[0031] When R5 and R6 are not hydrogen atoms, they are organic groups that are not Rf, and the organic groups are equivalent to the organic groups described above when R1 and R4 are organic groups that are not Rf. preferable.

When Y is a divalent organic group having two or more fluorine atoms, it is a polyfluoroalkylene group,
Polyfluoroxaalkylene groups (at least one ether bond exists between the carbon chains of the alkylene group), and polyfluorothioxaalkylene groups (at least one thioether bond exists between the carbon chains of the alkylene group) is preferred. Particularly, the moieties bonded to the silicon atoms at both ends are polymethylene groups (particularly dimethylene groups), and the intermediate moiety between them is a perfluoroalkylene group, a perfluorooxaalkylene group, or a perfluorothioxaalkylene group. Organic groups are preferred. The carbon number of these Y is 6 to 30, especially 6 to 1
6 is preferred.

Further, when Y is not a divalent organic group having two or more fluorine atoms, it is preferably an alkylene group, an oxaalkylene group, or a thioxaalkylene group. The number of carbon atoms is preferably 2 to 30, particularly preferably 2 to 16.

Specific examples of Rf, R1 to R6, and Y include the following specific examples of compound (A) and compound (B). The Rf group in the specific examples below is:
In particular, a polyfluoroalkyl group having a perfluoroalkyl group moiety represented by CnF2n+1CmH2m- (in this chemical formula, n is an integer of 3 to 16 and m is an integer of 2 to 4) is Particularly preferred as the group is CnF2n+1- (in this chemical formula, n is an integer of 3 to 16).

Specific examples of compound (A) and compound (B) are shown below. However, compound (A) and compound (B
) is not limited to these specific examples. In the chemical formula below, x, n, and m each represent an integer of 1 or more, X represents a hydrolyzable group, R represents an alkyl group, Rf represents a polyfluoroalkyl group, and RF represents a perfluoroalkyl group. In these chemical formulas, x is 2
-8, X is preferably a lower alkoxy group, R is a lower alkyl group, and Rf is preferably a dimethylene group having a perfluoroalkyl group.

Examples of compound (A).

[0037]

[Chemical formula 1]

[0038]

[Case 2]

[0039]

[Chemical formula 3]

[0040]

[C4]

[0041]

[C5]

[0042]

[C6]

[0043]

[C7]

[0044]

[Chemical formula 8]

[0045]

[Chemical formula 9]

Examples of compound (B).

[0047]

[Chemical formula 10]

[0048]

[Chemical formula 11]

Furthermore, in the present invention, a hydrolyzable silane compound (II) other than the fluorine-containing organosilane compound or a partial hydrolysis product thereof is used as a material for forming the second layer. The second layer below the first layer has the effect of improving the durability of the first layer and also improving the adhesion to the base material. This second layer is usually formed on the surface of the substrate. Hereinafter, this hydrolyzable silane compound (II) is converted into a compound (C
) Also called. This compound (C) is preferably a compound represented by the following formula (C).

(C) R7iR8jR9kSiX4-
i-j-k, where X is a hydrolyzable group, R7, R8,
R9 is independently hydrogen or an organic group having 1 to 16 carbon atoms (but not an organic group having 2 or more fluorine atoms),
i, j, k are independently 0, 1, 2, 3, and 0≦
Represents an integer satisfying i+j+k≦3.

When R7 to R9 are not hydrogen atoms, they are organic groups that are not Rf, and the organic groups are equivalent to the organic groups described above when R1 to R4 are organic groups that are not Rf. preferable. Especially preferred compound (C
) is a compound with i+j+k=0. Most preferred is tetraalkoxysilane. The use of silane compounds having only these hydrolyzable groups, especially their partial hydrolysis products, is excellent in terms of compatibility and adhesion with the first layer. Of course, a good second layer can also be formed by using this compound in combination with other silane compounds or by adding additional components described below. ,

Specific examples of compound (C) are shown below, but compound (C) is not limited thereto.

Tetramethoxysilane, tetraethoxysilane, tetra(n-propoxy)silane, tetra(i-
propoxy) silane, tetra(n-butoxy) silane,
Tetraalkoxysilanes such as tetra(sec-butoxy)silane and tetra(t-butoxy)silane.

Methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane,

γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(amino ethyl) -γ-
Aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane,

Glycidoxymethyltrimethoxysilane,
Glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycid xyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,

γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropyltripropoxysilane, γ-
Glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β -Glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-
Glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane,

(3,4-epoxycyclohexyl)methyltrimethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-
Epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltripropoxysilane, β-(3,4-epoxycyclohexyl)ethyltributoxysilane, β-(3,4-
epoxycyclohexyl)ethyltrimethyltrimethoxyethoxysilane,

γ-(3,4-epoxycyclohexyl)propyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)propyltriethoxysilane, δ
Trialkoxysilanes such as -(3,4-epoxycyclohexyl)butyltrimethoxysilane and δ-(3,4-epoxycyclohexyl)butyltriethoxysilane. Triacyloxysilanes such as methyltriacetoxysilane, vinyltriacetoxysilane, phenyltriacetoxysilane, and γ-chloropropyltriacetoxysilane.

Methyltriphenoxysilane, γ-glycidoxypropyltriphenoxysilane, β-(3,4-
Triphenoxysilanes such as epoxycyclohexyl)ethyltriphenoxysilane.

Dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane,

γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-
Aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane,

[
Glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldimethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β -Glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxy silane,

γ-Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycid Xypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, Dialkoxysilanes such as γ-glycidoxypropylphenyldiethoxysilane.

Diacyloxysilanes and diphenoxysilanes such as dimethyldiacetoxysilane and γ-glycidoxypropylmethyldiphenoxysilane.

In the present invention, the first layer, which is the outermost layer of the surface treatment layer, is a layer obtained by treatment with the fluorine-containing organosilane compound (I) or its partial hydrolysis product. As the composition for forming this layer, it is preferable to use a solution or dispersion containing the fluorine-containing organosilane compound (I) or a partially hydrolyzed product thereof.

In addition to the solvent and dispersant, other additives may be added to the composition. The additive includes an acid for carrying out the above-mentioned hydrolysis. Moreover, hydrolyzable silane compound (II) and its partial hydrolysis products can also be added to this composition. The amount added is not particularly limited, but it is preferably at most the same weight, particularly at most 50% by weight, based on the total weight of the fluorine-containing organosilane compound (I) and its partially hydrolyzed product.

Furthermore, fine particles of metal oxides such as silica, aluminum oxide, and zirconium oxide, especially ultrafine particles in sols such as silica sol and alimina sol, other filler components, epoxy resins, unsaturated polyester resins, polyurethane resins, ( Binder components such as meth)acrylates can also be added. Also, film forming properties (workability) of the composition
Surfactants can also be added to increase the

In such a composition, the amount of additive components other than the solvent and dispersant can be changed depending on the purpose, but it is usually 40 parts by weight or less, especially 10 parts by weight, based on 100 parts by weight of the total silane compound. The following are preferred. When using a filler component as an additive, 0.1 to 20 parts by weight,
Particularly preferred is 1 to 10 parts by weight. When a binder component is used, it is preferably 10 parts by weight or less, particularly 0.5 to 5 parts by weight. Excessive addition of these additives is undesirable because it reduces the water repellency, abrasion resistance, etc. of the present invention.

The above composition may be applied directly to the substrate to be coated by hand wiping or the like, but it is preferable to use it in the form of a solution or dispersion for reasons such as ease of application. The total amount of all silane compounds contained in this solution or dispersion using an organic solvent or the like is determined by taking into account film formation properties (workability), stability, film thickness, and economic efficiency, but it is 0.1
Preferably it is 30% by weight. As the organic solvent, various solvents such as acetic acid esters, aromatic hydrocarbons, halogenated hydrocarbons, ketones, and ethers can be used. The solvent is not limited to one type, and it is also possible to use a mixed solvent of two or more types.

The second layer, which is the lower layer in contact with the outermost layer, is a layer obtained by treatment with the hydrolyzable silane compound (II) or its partial hydrolysis product. The composition for forming this layer is a hydrolyzable silane compound (II
) or a solution or dispersion containing a partial hydrolysis product thereof. In addition to the solvent and dispersant, other additives may be added to the composition. The solvents, dispersants, additives, etc. mentioned above can be used, and the amounts used are preferably in accordance with the above. Of course, this second composition contains the fluorine-containing organosilane compound (I)
Alternatively, it is a composition that does not substantially contain the partial hydrolysis product.

No special pretreatment is required for the surface treatment of the base material or the surface treatment for forming the first layer on the second layer. However, there is no particular problem in performing it depending on the purpose. For example, acid treatment with diluted hydrofluoric acid, hydrochloric acid, etc., alkaline treatment with sodium hydroxide, potassium hydroxide aqueous solution, etc., or discharge treatment with plasma irradiation etc. can be performed. can.

Each layer is formed by applying a liquid material containing an organic solvent containing the prepared composition to the surface by a conventional treatment method, such as brush coating, flow coating, spin coating, dip coating, spray coating, etc. Drying is performed in the atmosphere or nitrogen air, at room temperature, or by heating. When further firing is performed, the material is heated at a drying temperature or at an even higher temperature. When heating, it is preferable to set the temperature and time taking into consideration the heat resistance of the base material.

The thickness of each layer formed can be appropriately controlled by the composition concentration of the liquid containing the composition, coating conditions, heating conditions, etc. The first layer of the present invention has a relatively low refractive index and therefore also provides low reflectivity. If such an effect is expected, the thickness of the first layer may be controlled to a thickness at which optical interference occurs. In particular, in order to exhibit water repellency, the film thickness of the film should theoretically be at least a monomolecular layer, and taking economic effects into consideration, it is desirable that the film thickness be 2 μm or less as mentioned above.

A substrate having such a layer can be easily installed as an article or part of a transportation device. For example, train bodies, window glass, pantographs, etc.
It can be easily used for automobile (truck) bodies, windshields, rear glasses, side glasses, mirrors, bumpers, etc., ship bodies, window glasses, etc., aircraft bodies, window glasses, etc.

[0076] In such a surface-treated base material, water droplets adhering to the surface are repelled by the water repellency, and in particular, due to the interaction with the wind pressure received during operation, the water droplets move rapidly on the surface and accumulate as water droplets. This makes it possible to eliminate the negative effects caused by moisture. In particular, when used in transparent viewing areas such as various window glasses, it is extremely easy to secure a field of view due to the scattering of water droplets, leading to improved vehicle safety. Further, even in environments where water droplets freeze, it does not freeze, and even if it does freeze, it thaws extremely quickly. Furthermore, since there is almost no adhesion of water droplets, the number of periodic cleaning operations can be reduced, and cleaning is extremely easy, which is very advantageous in terms of maintaining aesthetic appearance.

[0077]

[Examples] The present invention will be explained in detail below using Examples, but the present invention is not limited to the Examples. The various evaluation methods implemented in the examples are as follows.

1. Water repellency 1-a) Contact angle with water was measured. Measurements were taken at five different locations on the surface of the base material, and the average value is shown. 1-b) After spraying water over the entire surface for about 1 hour from a nozzle held at a distance of 20 cm from the sample surface, water droplets remaining on the surface were observed with the naked eye and evaluated using the following evaluation criteria.

[0079] A: No water remains on the sample surface. B: A little water remains on the sample surface. C: Considerable water droplets remain on the sample surface. D: Water wets and spreads on the sample surface.

2. Abrasion resistance tester: Taber type rotary abrader (Toyo Seiki Seisakusho Co., Ltd.). Test conditions: wear wheel H-22, load 1kg, number of wear 3
00 times. A wear resistance test was conducted using the above method, and the water repellency after the test was evaluated.

3. Weather resistance test UV irradiation for 8 hours (70°C), humidity exposure for 4 hours (5
One cycle is the process of reducing the temperature to 0°C), and the process is carried out in 100 cycles. A weather resistance test was conducted using the method described above, and the water repellency after the test was evaluated.

4. Boiling test: Immersed in boiling water for 1 hour. Water repellency after the test was evaluated.

5. Compound used (a) (CH3O)3SiC2H4C6F12C2H
4Si(OCH3)3(b) (CH3O)2(CH3
)SiC2H4C6F12C2H4Si(CH3)(O
CH3)2(c) C8F17CH2CH2Si(OC
H3)3(d) Si(OCH3)4 (e) Epoxy resin (trade name "EP 827", manufactured by Yuka Shell Epoxy Co., Ltd.) (f) Methanol-dispersed silica sol (solid content 30% by weight)
, manufactured by Catalysts Kasei Co., Ltd.)

[Preparation of Processing Agent 1] In a flask equipped with a stirrer and a thermometer, (d) 78.5 g, methyl alcohol 1020.2 g, isopropyl alcohol 2
000.0g was added and stirred for 1 hour. While maintaining the temperature of this solution at 5° C., 37.2 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After completion of the dropwise addition, stirring was continued for 5 days while maintaining the liquid temperature at 25° C. to obtain Treatment Agent 1.

[Preparation of Processing Agent 2] In a flask equipped with a stirrer and a thermometer, (d) 75.0 g, (f)
10.9 g of methyl alcohol, 1203.5 g of methyl alcohol, and 2000.0 g of isopropyl alcohol were added, and the mixture was stirred for 1 hour. While maintaining the temperature of this solution at 5° C., 35.5 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After completion of the dropwise addition, stirring was continued for 5 days while maintaining the liquid temperature at 25° C. to obtain Treatment Agent 2.

[Preparation of Treatment Agent 3] Into a flask equipped with a stirrer and a thermometer, (a) 56.3 g, (c)
29.4g, (d) 43.9g mixed, methyl alcohol 1531.9g, isopropyl alcohol 7000g
．． Then, 8.9 g of sodium acetate was added and stirred for 1 hour. While maintaining the temperature of this solution at 5° C., 34.5 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After completion of the dropwise addition, stirring was continued for 5 days while maintaining the liquid temperature at 25° C. to obtain Treatment Agent 3.

[Preparation of Processing Agent 4] In a flask equipped with a stirrer and a thermometer, (a) 23.0 g, (b)
10.8g, (c) 30.0g, (d) 22.4g,
and (e) 13.6g mixed, 1708.9g methyl alcohol, 7000.0g isopropyl alcohol
g and stirred for 1 hour. While maintaining the temperature of this solution at 5° C., 23.6 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After completion of the dropwise addition, stirring was continued for 5 days while maintaining the liquid temperature at 25° C. to obtain Treatment Agent 4.

[Example 1] 10 cm x 10 cm (thickness 3
A glass plate of 11 mm) was immersed in a solution of treatment agent 1.
It was pulled up at a speed of m/min and heated at 80° C. for 10 minutes. After leaving this test piece at room temperature for 30 minutes, it was immersed in a solution of treatment agent 3 and pulled up at a speed of 11 cm/min.
A sample test piece was prepared by heating at 0° C. for 30 minutes. Table 1 shows the results of evaluating this test piece.

[Example 2] Tests and evaluations were conducted in the same manner as in Example 1, except that treatment agent 3 in Example 1 was changed to treatment agent 4. The results are also shown in Table 1.

[Example 3] Tests and evaluations were carried out in the same manner as in Example 1, except that Treatment Agent 1 in Example 1 was changed to Treatment Agent 2. The results are also shown in Table 1.

[Example 4] Example 1 except that treatment agent 1 in Example 1 was changed to treatment agent 2, and treatment agent 3 was changed to treatment agent 4.
Tests and evaluations were conducted in the same manner. The results are also shown in Table 1.

[Example 5] The treatment agent 1 in Example 1 was heated from 80°C for 10 minutes to 300°C for 30 minutes.
Tests and evaluations were conducted in the same manner as in Example 1 except that the time was changed to minutes. The results are also shown in Table 1.

[Comparative Example 1] 10 cm x 10 cm (thickness 3
A glass plate of 11 mm) was immersed in a solution of treatment agent 3.
A sample test piece was prepared by pulling up at a speed of m/min. Table 1 shows the results of evaluating this test piece.

[0094]

[Table 1]

[Example 6] The test piece obtained in Example 1 was immersed in the chemicals shown in Table 2 for 24 hours, taken out and immediately washed, and the appearance change and water droplet removability of the test piece were confirmed. . The results are shown in Table 2.

[0096]

[Table 2]

[Example 7] Two surface treatment layers were formed on the surface of a laminated front glass for an automobile using the method of Example 1. The thus obtained front laminated glass was attached to the front of an automobile. This automobile was subjected to a driving test for 4 hours during the day for one month, and the state of dirt and dust adhering to the front surface was observed with the naked eye on a daily basis, as well as the state of adhesion of water droplets in rainy weather.

[0098] As a result, no water stains due to dirt, dust or water droplets were observed, and even if they were occasionally observed, they were easily removed by wiping lightly with tissue paper. Additionally, in rainy weather, water droplets on the surface are repelled and quickly move away due to interaction with wind pressure from driving, ensuring visibility without the need for wipers. Furthermore, in driving tests in environments (0°C to -5°C) where water droplets adhering to untreated front laminated glass freeze, or where moisture in the air condenses and freezes on the windshield, No freezing was observed on the glass.

[0099] Next, under an even more severe low temperature environment (-10°C ~
-15°C), ice formation was observed on the windshield, but it thawed quickly, which was a significant difference compared to an untreated windshield.

[Example 8] A driving test was conducted by changing the front laminated glass of Example 7 to side glass and rear glass, and the same effects as in Example 7 were confirmed.

[Example 9] A driving test was conducted by changing the front laminated glass of Example 7 to side mirrors.
The same effect as in Example 7 was confirmed.

[0102]

INDUSTRIAL APPLICABILITY The substrate for transportation equipment, the article for transportation equipment, and the transportation equipment equipped with them according to the present invention have excellent effects as is clear from the examples. That is, 1. It has excellent water repellency and does not attract dust, dirt, water droplets, or water stains, and even if they do occur, they can be easily removed and block the negative effects of water. It is possible to do this, and cleaning can be simplified.

2. It has excellent water repellency and maintains its state semi-permanently. 3. It has excellent chemical resistance and is effective even when used along coastlines or on ships that come into direct contact with seawater. 4. It does not require any special pretreatment and is highly economical. 5. It can also be applied to transportation equipment articles that are already in common use. The above-mentioned effects cannot be expected with conventional materials, and it is expected that the range of application will be expanded to fields where it could not be used until now.

Claims (10)

[Claims] Claim 1: An article for transportation equipment comprising a base material having at least two surface treatment layers, or having the base material as a component, wherein the first layer, which is the outermost layer of the surface treatment layers, has at least two surface treatment layers. A layer obtained by treatment with a fluorine-containing organosilane compound (I) having the above organic group having a fluorine atom and a hydrolyzable group or a partial hydrolysis product thereof,
The second layer, which is the lower layer in contact with the outermost layer, is a hydrolyzable silane compound (II) other than the above-mentioned fluorine-containing organosilane compound.
Or an article for transportation equipment, which is a layer obtained by treatment with a partial hydrolysis product thereof. 2. The surface treatment layer is a second layer formed by treating the surface of the substrate with a hydrolyzable silane compound (II), a partial hydrolysis product thereof, or a composition containing at least one thereof. The surface of the second layer is then treated with a fluorine-containing organosilane compound (I), a partial hydrolysis product thereof, or a composition containing at least one thereof to form a first layer. , The article for transportation equipment according to claim 1. 3. The article for transportation equipment according to claim 1, wherein the substrate having the surface treatment layer is a substrate made of a transparent material. 4. The article for transportation equipment according to claim 3, wherein the base material is glass. 5. The article for transportation equipment according to claim 1, wherein the fluorine-containing organosilane compound (I) is a compound represented by the following formula (A) or (B). (A) X3-a-b(R1)a(R2)bSi-Y
-Si(R3)c(R4)dX3-c-dHowever, X
is a hydrolyzable group, R1, R2, R3, R4 are independently hydrogen or an organic group having 1 to 16 carbon atoms, a and b are independently 0
, 1, 2, and integers satisfying 0≦a+b≦2; c, d are independently 0, 1, 2, and 0≦c+d
an integer satisfying ≦2, and Y represents a divalent organic group, and Y or at least one of R1 to R4 present is an organic group having two or more fluorine atoms. (B) (Rf)eR5gR6hSiX4-e-g-
h However, X is a hydrolyzable group, Rf is an organic group having 2 or more fluorine atoms, R5 and R6 are independently hydrogen or an organic group having 1 to 16 carbon atoms, e is 1, 2, 3, g, h
are independently 0, 1, 2, 3, and 1≦e+g+h
Represents an integer that satisfies ≦3. Claim 6: The hydrolyzable group is a hydrolyzable group selected from a halogen atom, an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group, an aminoxy group, an amide group, an acid amide group, and a ketoximate group. Articles for transportation equipment. 7. In formula (A), Y is a divalent organic group having two or more fluorine atoms, or there is an organic group bonded to a silicon atom, and at least one of the organic groups is present.
5. is an organic group having a polyfluoroalkyl group having 3 or more carbon atoms, and in formula (B), Rf is an organic group having a polyfluoroalkyl group having 3 or more carbon atoms.
Articles for transportation equipment. 8. In formula (A), Y is a polyfluoroalkylene group, or there is an organic group bonded to a silicon atom, and at least one of the organic groups has a perfluoroalkyl group having 3 or more carbon atoms. 6. The article for transportation equipment according to claim 5, wherein Rf in formula (B) is an organic group having a perfluoroalkyl group having 3 or more carbon atoms. 9. The article for transportation equipment according to claim 1, wherein the hydrolyzable silane compound (II) is a compound represented by the following formula (C). (C) R7iR8jR9kSiX4-i-j-kHowever, no), i, j, k
are independently 0, 1, 2, 3, and 0≦i+j+k
Represents an integer that satisfies ≦3. 10. The hydrolyzable group is a halogen atom, an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group,
The article for transportation equipment according to claim 9, wherein the hydrolyzable group is selected from an aminoxy group, an amide group, an acid amide group, and a ketoximate group.