JP3210045B2 - Surface treated substrate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a substrate having a surface to which little water droplets adhere or to which the adhered water droplets are easily removed.

[0002]

2. Description of the Related Art Various substrates and various substrates having a surface treatment layer have been used in various fields, but the adverse effect of water on the surface has become a problem.

[0003] For example, the surface of outer panels, windowpanes, mirrors, exterior members such as surface materials of display devices, interior members such as surface materials of instrument panels, and the surface of other articles in transportation equipment such as trains, automobiles, ships, and aircrafts are always present. It is preferably clean. If raindrops, dust, dirt, etc. adhere to the surface of the transport equipment article, or if moisture condenses due to the influence of humidity and temperature in the atmosphere, its appearance is impaired. It is, or a surface to be viewed directly by the human eye, and there is on the surface a person is in direct contact, also occur discomfort and health problems.

[0004] Furthermore, the original function of the article for transportation equipment is significantly reduced. In particular, when the transport equipment article is an article that requires transparency and transparency (for example, a window glass, a mirror, etc.), the reduction in transparency and transparency can achieve the original purpose of the article. It has such.

[0005] Means for removing water droplets (eg, wiping, removal with a wiper) can occasionally cause fine scratches on the surface. There is also possible to even more significant in the foreign particles thus such wounds are accompanied by water drops. Further, it is well known that when moisture adheres to the glass surface, the glass component elutes in the moisture, causing so-called burning, which erodes the surface. If strong friction is applied to remove this burn, fine irregularities are likely to occur.
The see-through part made of glass with severe burns or glass with fine irregularities on the surface has its original function deteriorated,
Inconvenience Ji that raw <br/> in terms of scattering of light is intense field secured at its surface.

[0006] In addition, moisture has a detrimental effect on the surface of transport equipment articles, and promotes damage, contamination, coloring, corrosion, etc., as well as electrical, mechanical and optical properties of transport equipment articles. In some cases, it may cause changes in traits or the like. The adverse effects of this type of water are not limited to articles for transportation equipment, but are a problem in various fields such as articles for construction and construction, articles for electric and electronic equipment.

[0007] Under such circumstances, there is a strong demand for imparting properties such that water droplets are less likely to adhere to the surface of the base material or are easily removed (hereinafter, these are simply referred to as water droplet removing properties). Conventionally, in order to make the surface water-removable, for example, a surface treatment agent that is directly applied, such as a silicone wax or a silicone oil composed of an organopolysiloxane or a surfactant, has been proposed.

However, many of these require pretreatment accompanying the coating, and there is a problem that coating unevenness tends to occur during coating. In addition, since the treatment agent itself has low adhesion to the base material, it has not been possible to satisfy the long-term sustainability of the water droplet removal property, and its application range has been limited.

In consideration of the influence of moisture, it is necessary to take measures against not only various base materials to be manufactured in the future but also various base materials already used. In this case, it is necessary to impart water droplet removability only by directly applying to various substrates at normal temperature. For example, when considering such a process for an automobile windshield that has already been used, it is not economically possible to replace the windshield of each automobile, and it is also realistic to bake that part after coating. Is impossible. From this point of view, it is difficult to cope with the conventionally proposed treating agents.

[0010]

SUMMARY OF THE INVENTION In the course of research and examination of a treatment agent capable of solving the drawbacks of the prior proposals, the present inventor has found that excellent water droplet removal properties which can be applied to various types of base materials. Finding a treating agent that develops, and furthermore, various substrates treated with the treating agent as a substrate having water droplet removing properties,
The present invention has been confirmed to be extremely suitable for transportation equipment or construction / building equipment, and has led to the present invention.

Accordingly, an object of the present invention is to provide a base material which has a water droplet removing property and is excellent in abrasion resistance, chemical resistance, and weather resistance, and the effect of which is semipermanently maintained.

[0012]

Means for Solving the Problems The present invention is the following invention which has achieved the above object. A surface-treated substrate having at least two treated surface layers, the following compounds first layer is the outermost layer of the surface treatment layer may form a surface contact angle values for the water is 70 degrees or more ( a layer obtained by treatment with I), the second layer is a lower layer in contact with the outermost layer polyphenylene
A surface-treated substrate, which is a layer obtained by treating with a isocyanatosilane compound (II) having no fluoro organic group . Compound (I): an isocyanate group or a hydrolyzable group
Having at least one bonded silicon atom,
Reactive silane having at least one polyfluoro organic group
Compound.

In the present invention, the contact angle value with water is 70.
Degrees at a compound capable of forming a surface (I) [hereinafter simply referred to as compound (I)] is Ru essential component der to express the water droplet removal property. However, in consideration of the adhesion to the second layer described later, those having a reactive group are preferable. Here, the reactive group is a halogen atom, an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group, an aminoxy group, an acid amide group, a ketoxime group, a hydroxyl group,
A functional group such as an unsaturated hydrocarbon group such as a mercapto group, an epoxy group, a glycidyl group, a vinyl group or an allyl group, a carboxy group, or a functional group having an atom capable of hydrogen bonding (eg, an oxygen atom or a nitrogen atom); means.

Compound (I) has a contact angle value with water of 7
A compound capable of forming a surface is 0 degrees or more, at least one have the hydrophobicity of the organic group. And the hydrophobic organic group is a polyfluoroorganic group, such as a polyfluoroalkyl group or polyfluoroalkylene group. As these polyfluoro organic groups, a polyfluoro organic group as exemplified later, particularly a polyfluoro hydrocarbon group is preferable.

As a result of intensive studies, it has been found that an isocyanate silane compound in which at least one isocyanate group is directly bonded to a silicon atom or a hydrolyzable silane compound in which at least one hydrolyzable group is directly bonded to a silicon atom, It has been found that compounds having a hydrophobic organic group such as described above are particularly effective as compound (I) in the present invention.

Hereinafter, the "reactive silane compound" is used as a general term for both the "hydrolyzable silane compound" and the "isocyanate silane compound". The “hydrolyzable silane compound” is a “hydrolyzable silane group” in which at least one hydrolyzable group is bonded to a silicon atom (“S
IX "and X are compounds having at least one hydrolyzable group). "Isocyanate silane compound"
“Isocyanate silane group” in which at least one isocyanate group is bonded to a silicon atom (“SI-NC
O "). The “reactive silane group” (represented by “SI-Z”) is used as a general term for both the “hydrolyzable silane group” and the “isocyanate silane group”.

Although there is a view that the "isocyanate silane group" is a kind of the "hydrolyzable silane group" (that is, the isocyanate group bonded to the silicon atom is considered to be a kind of the hydrolyzable group). In the present invention, both are separate. That is, in the present invention, an isocyanate group bonded to a silicon atom is not considered to be a hydrolyzable group (even though the isocyanate group is actually hydrolyzable).

Preferred as the reactive silane compound is a compound having one or two reactive silane groups. More preferred as the compound are a compound represented by the following formula (A) (also referred to as compound A), a compound represented by the following formula (B) (also referred to as compound B), and polyfuran.
Isocyanate silane compounds having no organic organic group (I
In the case of I), tetraisocyanatesilane is further added.

(A) (Z) _3-ab (R ¹ ) _a (R ² ) _b SI-Y-SI (R ³ ) _c (R ⁴ ) _d (Z) _3-cd where R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group having 1 to 21 carbon atoms; Y is a divalent organic group;
Is an isocyanate group or a hydrolysable group, a and b are each independently 0, 1 or 2, and an integer satisfying 0 ≦ a + b ≦ 2, and c and d are each independently 0, 1 or 2 and 0 Represents an integer satisfying ≦ c + d ≦ 2.

(B) (R ⁵ ) _e (R ⁶ ) _g (R ⁷ ) _h SI (Z) _4-egh , wherein R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a carbon atom having 1 to 21 carbon atoms. Wherein Z is an isocyanate group or a hydrolyzable group, and e, g, and h are each independently 0, 1 or 2, and an integer satisfying 1 ≦ e + g + h ≦ 3. Represent.

[0021] Compound (I), Ru reactive silane compound der having at least one hydrophobic organic group. In particular, Compound A, of B, Ru compound der least one organic group is a polyfluoroorganic group to exhibit an excellent water droplet removal property. In this case, Z of the reactive silane group may be an isocyanate group or a hydrolyzable group.

On the other hand, an isocyanate silane compound (II) having no polyfluoro organic group (hereinafter referred to as isocyanate
Also referred to as tosilane compound (II). ) Represents compounds A and B
Among them, a compound in which Z of the reactive silane group is an isocyanate group and tetraisocyanate silane are preferable .
Lee Socia sulfonate silane compound (II), have Na has a polyfluoro <br/> organic group. For example, the organic groups of compounds A and B in which Z is an isocyanate group are preferably an alkyl group having 6 or less, particularly 4 or less, or an alkylene group having 8 or less, particularly 6 or less carbon atoms.

However, the number of carbon atoms, hydrophobicity and the like are relative and vary depending on the type of compound. Therefore,
As long as the first layer has a higher contact angle to water than the second layer, the surface of the second layer formed by the treatment with the isocyanate silane compound (II) has a contact angle to water of 70 degrees or more. It may be. That is, in some cases, the isocyanate silane compound (II) may be a compound capable of forming a surface having a contact angle with water of 70 ° or more.

Hereinafter, the compound (I) will be described in more detail. When the compound (I) is an isocyanate silane compound, this compound [hereinafter also referred to as compound (I-NCO)] needs to be a compound capable of forming a surface having a contact angle value with water of 70 ° or more. That is, the contact angle of water on the surface treated with this compound (I-NCO) must be 70 degrees or more. Compound (I-NCO)
Refers to the surface of the second layer to which the compound (I-NCO) is chemically or physically bonded. Since the isocyanate group is reactive, it is considered that the compound (I-NCO) is mainly bonded to the surface of the second layer by a chemical reaction. That is, it is considered that the isocyanate group is changed in the bonded state. For example, an isocyanate group is considered to react with a silanol group on the glass surface, and a silanol group generated by elimination of the isocyanate group is considered to react.

The compound (I-NCO) has excellent surface water-removability, abrasion resistance, chemical resistance, weather resistance, etc. due to the reactivity of the isocyanate group and the effect of the silicon atom directly bonded to the isocyanate group. It seems that the performance of this is expressed. Further, as described later, these performances can be further improved by selecting an organic group. It is desirable that the number of isocyanate groups bonded to one silicon atom is two or more in terms of bonding to the second layer.

Next, when the compound (I) is a hydrolyzable silane compound, this compound [hereinafter also referred to as compound (IX)] is a compound capable of forming a surface having a contact angle with water of 70 ° or more. Needs to be That is, the contact angle value of water on the surface treated with this compound (IX) is 7
It must be at least 0 degrees. The surface treated with the compound (IX) refers to the surface of the second layer to which the compound (IX) is chemically or physically bonded. Since the hydrolyzable group is reactive, it is considered that compound (IX) is bonded to the surface of the second layer mainly by a chemical reaction. That is, it is considered that the hydrolyzable group is changed in the bonding state.

The hydrolyzable group in the compound (IX) is a group directly bonded to a silicon atom. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group, an aminoxy group, an acid amide group, and a ketoximate group. Preferably, a hydrolyzable group such as an alkoxy group, an alkoxy-substituted alkoxy group, and an acyloxy group is bonded to a silicon atom via an oxygen atom. The number of carbon atoms of these hydrolyzable groups is preferably 8 or less, particularly preferably 4 or less. Most preferably, it is an alkoxy group having 1 to 4 carbon atoms.

The compound (IX) has excellent surface water-removability, abrasion resistance and the like due to the reactivity of the hydrolyzable group and the effect of the silicon atom directly bonded to the hydrolyzable group.
It is thought to exhibit properties such as chemical resistance and weather resistance. Further, as described later, these performances can be further improved by selecting an organic group. 1 in terms of connectivity to the second layer
The number of hydrolyzable groups bonded to silicon atoms is desirably two or more.

The compound (IX) may be used as it is, or may be used as a partial hydrolysis product by hydrolysis. The partially hydrolyzed product of compound (IX) is a compound having a silanol group or the like formed by partially hydrolyzing these silane compounds in water or an acidic aqueous solution or two or more molecules by the reaction of the silanol group. Are condensed. As the acid, for example, hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid and the like can be used.

[0030] These compounds (I-NCO) and the compound (I-X) is a compound A, a compound contact angle values with water can form a surface is at least 70 degrees of the B.
Such a compound A, B [hereinafter, compound (I-
A), also referred to as Compound (I-B)] is present R ¹ ~
R ⁷ is an organic group, these at least one is polyphenylene
Ruoro or Y is an organic radical is a compound polyfluoro organic group. Either may be a polyfluoro organic group. Z is preferably two or more per silicon atom. The hydrophobic group is effective for removing water droplets, and it is considered that the more Z groups, the stronger the bond to the second layer.

When R ^{1 to} R ⁷ are organic groups, examples of the organic groups include hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, and aryl groups, and halogenated carbon groups such as chloroalkyl groups and polyfluoroalkyl groups. Ester bond, ether bond, thioether bond, imino bond, amide bond, in a (halogenated) hydrocarbon group having a hydrogen group, a hydroxyl group, an epoxy group, an amino group, a mercapto group, a carboxy group, or another functional group and a carbon chain. (Halogenated) hydrocarbon groups having a urethane bond or other linking bonds are preferred. Among these, the organic group which is a hydrophobic group is a long-chain hydrocarbon group and the following polyfluoroalkyl group. As the long-chain hydrocarbon group, an alkyl group or an alkenyl group having 7 to 20 carbon atoms is preferable. As the organic group which is not a hydrophobic group, a lower alkyl group, that is, an alkyl group having 1 to 4 carbon atoms is preferable.

The reduction compound (I-A), Compound (I-B) are small
It is a reactive silane compound having at least one polyfluoro organic group . That is, in compound (IA), Y
Is a polyfluoroorganic group or a compound wherein at least one of R ^{1 to} R ⁴ present otherwise is a polyfluoroorganic group. Any of Y and at least one of R ^{1 to} R ⁴ present may be a pororofluoro organic group.

Compound (IB) is a compound in which at least one of R ^{5 to} R ⁷ present is a polyfluoro organic group . In these cases, the organic group which is not a polyfluoro organic group is preferably the above-mentioned hydrocarbon group which is not a hydrophobic group. Note that the polyfluoro organic group is preferably bonded to a silicon atom by a carbon atom having no fluorine atom (for example, a methylene group).

When Y is a polyfluoro organic group,
Examples of the valent organic group include a polyfluoroalkylene group, a polyfluorooxaalkylene group (having at least one ether bond in the middle of the carbon chain of the alkylene group), and a polyfluorothiaalkylene group (the middle of the carbon chain of the alkylene group). In which at least one thioether bond is present). In particular, the portion bonded to the silicon atoms at both ends is a polymethylene chain (particularly, a dimethylene group), and the intermediate portion thereof is a perfluoroalkylene group,
A divalent organic group that is a perfluoroxaalkylene group is preferred. The carbon number of Y is preferably 6 to 30, particularly preferably 6 to 16.

When Y is not a polyfluoro organic group, it is preferably an alkylene group, an oxaalkylene group or a thiaalkylene group. Its carbon number is preferably 2 to 30, particularly preferably 2 to 12.

When any of R ^{1 to} R ⁷ is a polyfluoro organic group, it may be a polyfluoroalkyl group, a polyfluorooxaalkyl group, a polyfluorothiaalkyl group, or a carbon such as an alkylene group. An organic group (bonded to a silicon atom at the other end of the hydrocarbon group) in which a hydrogen group is bonded by an ester bond or another linking bond as described above is preferable. The polyfluoroalkyl group and the polyfluorooxaalkyl group are preferably groups in which the end bonded to the silicon atom or its periphery is an alkylene group (particularly, a dimethylene group) and the other part is perfluoro.

The perfluoro moiety of the monovalent organic group is preferably a perfluoroalkyl group having 3 or more carbon atoms, a perfluorooxaalkyl group or a perfluorothiaalkyl group, and particularly preferably a perfluoroalkyl group having 3 to 16 carbon atoms. Is preferred.

Specific examples of Y and R ^{1 to} R ⁷ are in the following specific examples of compound A and compound B. Especially as _the R _f group in the following specific _{examples, C n F 2n + 1 C} m H 2m - (n is 3 to 12 integer in this formula, m is an integer of 2 to 4)
A polyfluoroalkyl group having a perfluoroalkyl group portion represented by the following is an R _F group in the following specific examples,
In particular, C _n F _{2n + 1-} (where n is 3 to
16 integers) are preferred.

Compound (IA) and Compound (IB)
Are shown below. However, compound (IA) and compound (IB) are not limited to these specific examples. In the following chemical formulas, n and m each represent an integer of 1 or more, R represents an alkyl group, R _f represents a polyfluoroalkyl group, and R _F represents a perfluoroalkyl group. In these chemical formulas, R preferably has 1 to 12 carbon atoms, and _Rf is preferably an ethyl group having a perfluoroalkyl group at a terminal. Z is an isocyanate group or a hydrolyzable group.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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As described above, two or more kinds of the reactive silane compounds as the compound (I) can be used in combination. However, it is better to avoid mixing an isocyanate silane compound and a hydrolyzable silane compound, for example, by mixing and using the compound (I-NCO) and the compound (IX) together. This is because the isocyanate group and the hydrolyzable group may react, and the life of the treating agent is shortened.

Further, in order to enhance the surface treatment effect of the compound capable of forming a surface having a contact angle with water of 70 ° or more in the present invention, the contact angle with water is set at 70 °.
It is preferred to use an organopolysiloxane with a compound capable of forming a surface having a degree or higher. What is called a silicone oil or a modified silicone oil is suitable as the organopolysiloxane. Hereinafter, this organopolysiloxane is referred to as compound C. The compound C preferably has a polymerized unit represented by the following formula (C).

(C) [—SIR ⁸ (CH ₃ ) —O—] In this formula, R ⁸ represents a monovalent organic group having 1 to 16 carbon atoms. The organic group R ⁸ is preferably the same organic group as R ^{1 to} R ⁷ described above, and particularly preferably a lower alkyl group.

Compound C is a compound capable of forming a surface having a contact angle with water of 70 ° or more, particularly the above-mentioned compounds (IA) and (IB), which are capable of removing water droplets from the coating and having resistance to water. Improves abrasion. Compound C may be added to the composition for surface treatment as it is, or may be added after being hydrolyzed with an acid such as sulfuric acid, hydrochloric acid, or acetic acid. The kinematic viscosity of Compound C is preferably determined in consideration of the combination with other compounds, and particularly, the kinematic viscosity at 25 ° C. is preferably 0.5 to 1000 centistokes.

Specific examples of the compound C are shown below, but the compound C is not limited thereto. M in these equations,
n, k, and j represent integers.

[0056]

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[0057]

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In the present invention, the composition for forming the first layer for treating the surface of the second layer has a contact angle value with water of 70.
A compound capable of forming a surface having a degree of degree or higher, particularly preferably the compounds (IA) and (IB) as described above, is an essential component. The mixing ratio of these compounds is arbitrary. In addition, when compound C is added, the ratio of addition to other components is arbitrary, but preferably the addition amount is 1 to 40% by weight. If the added amount of the compound C is too large, not only does the abrasion resistance decrease, but also a sticky feeling is left when touching the surface, and if it is too small, the abrasion resistance and workability may not be sufficient.

Compound C interacts with other components (for example, compounds (IA) and (IB) as described above) to improve the water droplet removal property of the film and the durability of the film. Contribute.
Although the detailed mechanism is unknown, compound C is intricately entangled with other components, and as a result, the microscopic distribution of various organic groups present on the surface, particularly polar groups and ionic bonds, is controlled, and water droplets are removed. It is considered that an optimal surface structure is achieved.

It is believed that this entanglement of the molecule with the other selected components has contributed significantly to further increasing durability. In addition, any compound capable of forming a surface having a contact angle value with water of 70 ° or more is a substance having a low surface free energy, and a free compound partially present in the coating film moves through the extremely surface layer. Therefore, it is considered that reducing the frictional resistance on the surface is also a part of the reason why the wear resistance is good.

Other compounds and additives may be added to the treating agent of the present invention according to the purpose. Additives etc. may be selected in consideration of reactivity with each component, compatibility, for example, silica,
Ultrafine particles of various metal oxides such as alumina, zirconia, and titania, and various resins can be added. If coloring is necessary, dyes, pigments, and the like can be added. The amount of addition may be about 0.01 to 20% by weight based on the total weight of the other components, and excessive addition is undesirable because it lowers the water drop removal property and the abrasion resistance of the present invention.

The above composition may be directly applied to the second layer to be coated by hand wiping or the like, or may be dissolved or diluted with an organic solvent to prepare a solution and use it. . In the solution using the organic solvent, the total amount of the components contained is determined in consideration of the moldability (workability), stability, film thickness, and economy of the film.
It is preferably about 30% by weight.

As the organic solvent, various organic solvents such as acetates, aromatic hydrocarbons, halogenated hydrocarbons, ketones, ethers and alcohols can be used. However, when compounds A and B have an isocyanate group, those having a reactive functional group (such as a hydroxyl group) are not desirable. Accordingly, alcohols are not suitable for the compound (I-NCO), but there is no particular limitation for the compound (IX). The diluting solvent is not limited to one kind,
Mixed solvents of more than one kind can also be used.

In the treatment of the surface of the second layer, no special pretreatment is required. The formation of the film is performed by applying a liquid material containing the prepared composition to the surface by a usual method, for example, brushing, flow coating, spin coating, dip coating, spray coating, etc., in the air or It may be dried in a nitrogen stream.

In particular, excellent performance is exhibited only by drying in the atmosphere, but there is no problem in heating for the purpose of increasing the drying speed. The heating temperature is preferably about 50 to 250 ° C., and the heating time is suitably about 5 to 60 minutes. If heating is necessary, the temperature and time may be set in consideration of the heat resistance of the substrate.

The thickness of the first layer formed by this surface treatment is not particularly limited, but is preferably extremely thin. The preferred film thickness is 2 μm or less. Also,
The lower limit is the monolayer thickness.

Next, an isocyanate silane compound (I
The I) and the second layer formed by the processing will be described.

In the present invention, an isocyanate silane compound (II) is used as a material for forming the second layer. The second layer below the first layer dramatically improves the durability of the first layer and also has the effect of increasing the adhesion to the substrate. This second layer is usually formed on the surface of the substrate, but there is no problem even if there are various films obtained by a vapor deposition film, a sputtered film, a wet method or the like on the substrate surface.

The isocyanate silane compound (II) for forming the second layer is a compound in which an isocyanate group is directly bonded to a silicon atom in the same manner as the above-mentioned compound (I-NCO). Due to the effect of the silicon directly bonded, it is firmly bonded to the first layer and the lower layer (for example, a base material), and contributes to improvement of wear resistance. Therefore, the greater the number of isocyanate groups directly bonded to silicon atoms per silicon atom, the better.

[0070]

Preferred compounds as the isocyanate silane compound (II) are compounds of compounds A and B wherein Z is an isocyanate group [hereinafter referred to as compound (II-
A), compound (II-B)], and tetraisocyanate silane. Preferably, a Te Tiger isocyanate silane.

When the isocyanate silane compound (II) is the compound (II-A) or the compound (II-B), it may have at least one organic group bonded to a silicon atom. the organic group <br/> phrases in polyfluoroorganic group, particularly a hydrocarbon group. Most preferred are a lower alkyl group and an alkylene group having 6 or less carbon atoms. Compound (I-NCO) has a polyfluoro organic group
However , the organic groups of the compound (II-A) and the compound (II-B) may be those having relatively lower hydrophobicity,
In some cases, it may be a long-chain hydrocarbon group.

In particular, considering the adhesion to the first layer and the lower layer (for example, a base material), the larger the number of isocyanate groups bonded to the silicon atom, the better. For the compound (II-A), the formula (A) In the compound (II-B), the compound of a + b = 0 and c + d = 0 is e + g + in the formula (B).
Compounds with h = 0 are preferred.

Specific examples of the isocyanate silane compound (II) are shown below.
I) is not limited to these. P in these formulas represents an integer, and 2 to 8 is preferable.

[0075]

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[0076]

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[0077]

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As the treating agent for forming the second layer of the present invention, it is desirable to use a solution or a dispersion containing the isocyanate silane compound (II) as an essential component. In addition to the solvent and the dispersant, other additives can be added to the composition. As the solvent, those described for the compound (I-NCO) and the like can be used. Specific examples of the additive include a filler such as the above-described ultrafine particles of a metal oxide, a binder component, and a surfactant. The above-mentioned ratios are also appropriate for their use ratio. It is also desirable that the used amount is the same as the above.

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

The second layer is formed by applying a liquid material comprising an organic solvent containing the prepared composition to the surface by a usual treatment method, for example, brushing, flow coating, spin coating, dip coating, spray coating. And drying at room temperature or by heating in the air or in a nitrogen stream.
Drying at room temperature is sufficient, but when drying by heating, the temperature and time may be set in consideration of the heat resistance of the substrate. However, heating and drying at an excessively long time and at a high temperature adversely affects the adhesion to the first layer.

The thickness of the second layer formed by this surface treatment is not particularly limited, but may be extremely thin. The preferred film thickness is 2 μm or less, like the first layer.
The lower limit is the thickness of the monolayer. An excessively thick film thickness is not preferable in terms of appearance quality and economy.

The thickness of each layer to be formed can be appropriately controlled by the composition concentration of the liquid containing the composition, coating conditions, heating conditions, and the like. The first layer of the present invention has a relatively low refractive index, and therefore also has 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, the film thickness of the coating film should theoretically be at least a monomolecular layer in order to exhibit water droplet removability, and preferably 2 μm or less in consideration of the economical effect.

The substrate to which the present invention can be applied is not particularly limited. For example, there are metals, plastics, glass, ceramics, other inorganic and organic materials, or combinations thereof (composite materials, laminated materials, and the like). The surface of the substrate may be a surface of a material different from the surface of the substrate, such as the surface of a coated metal plate or the surface of a surface-treated layer of surface-treated glass, as well as the substrate itself. Further, the shape of the base material is not limited to a flat plate, and may be any shape according to the purpose, such as a shape having a curvature over the entire surface or a part thereof.

Particularly suitable substrates in the present invention are glass,
It is a base material made of a transparent material such as plastic, and an appropriate article is an article using them and utilizing transparency. Therefore, the base material of the present invention can be used
Particularly desirable as a building article.

The transport equipment articles include outer plates of transport equipment such as trains, buses, trucks, automobiles, ships, and aircrafts,
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. The article may consist only of the surface-treated substrate or may incorporate the 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.

Examples of articles for transportation equipment include bodies of trains, windows, pantographs, etc., bodies of automobiles, buses, trucks, etc., windshields, side glasses, rear glasses, mirrors, bumpers, etc., bodies of ships, window glasses, etc. A body of an aircraft or the like, a window glass, or the like can be given.

In such substrates 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, the field of view secured greatly facilitated by scattering of water drops in applications in phantom field portion such as various window glass.
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.

Also, the building and building articles are articles that are attached to a building, articles that are already attached to a building, or building articles, furniture that are not attached to a building, but are used with it. Refers to building articles such as furniture and a base material (such as a glass plate) that is a component of those articles.

More specifically, various types of roofs including window glass plates, window glass, roof glass plates and glass roofs, glass plates for doors and doors into which they are fitted, glass plates for partitions, glass plates for greenhouses And greenhouses, transparent plastic plates used in place of glass and the above-mentioned architectural articles (window materials, roofing materials, etc.), wall materials made of ceramic, cement, metal and other materials, mirrors and so on Furniture, display shelves and glass for showcases.

The article may consist only 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, the water droplets in contact with the surface are repelled and hardly adhere due to the water droplet removing property. Even if they adhere, the amount of the water droplets is small, and the adhered water droplets can be easily removed. is there. In addition, it does not freeze even in an environment where water droplets freeze, and even if it freezes, thawing is extremely fast. Furthermore, since there is almost no adhesion of water droplets, the number of regular cleaning operations can be reduced, and the cleaning is extremely easy and is very advantageous from the viewpoint of aesthetic protection.

[0092]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples and the like, but the present invention is not limited to these examples. Various evaluation methods used in the examples are as follows.

1. 1-a) The contact angle of a water droplet having a size of 1 mm in diameter was measured. Measurements were made at five different locations on the surface, and the average value was 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 visually observed and evaluated according to the following evaluation criteria.

A: No water remains on the sample surface. B: Some water remains on the sample surface. C: Water considerably remains on the sample surface. D: Water spreads on the sample surface.

2. Abrasion resistance tester: Taber type rotary abraser [manufactured by Toyo Seiki Seisaku-sho, Ltd.]. Test conditions: wear wheel H-22, load 1 kg, wear frequency 50
0 times. The abrasion resistance was carried out by the above test method, and the water repellency after the test was evaluated.

3. Weathering test UV irradiation was performed for 8 hours (70 ° C) and wet exposure was performed for 4 hours (5 hours).
(0 ° C.) as one cycle, and 200 cycles. The weather resistance test was performed by the above method, and the water drop removal property after the test was evaluated.

4. Boiling test I was immersed in boiling water for 1 hour. The water drop removal after the test was evaluated.

5. Compounds used (a) C ₉ F ₁₉ C ₂ H ₄ SI (OCH ₃ ) ₃ (b) (CH ₃ O) ₃ SIC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ SI (O
CH ₃ ) ₃ (c) C ₉ F ₁₉ C ₂ H ₄ SI (NCO) ₃ (d) (OCN) ₃ SIC ₂ H ₄ SI (NCO) ₃ (e) SI (NCO) ₄

(F) SI (OCH ₃ ) ₄ (g) CH ₃ SI (OCH ₃ ) ₃ (h) CH ₃ SI (NCO) ₃ (I) C ₈ H ₁₇ SI (NCO) ₃ (j) (CH) ₃ ) ₂ SI (NCO) ₂

(K) Methanol-dispersed silica sol (solid content: 30% by weight, manufactured by Catalyst Chemical Industry Co., Ltd.) (l) Dimethylpolysiloxane having a kinematic viscosity of 50 centistokes (KF96 manufactured by Shin-Etsu Chemical Co., Ltd.) (m) Modified dimethylpolysiloxane having a kinematic viscosity of 42 centistokes having hydroxyl groups at both ends (KF6001 manufactured by Shin-Etsu Chemical Co., Ltd.) (n) Modified dimethylpolysiloxane having a kinematic viscosity of 50 centistokes having a carboxyl group (Shin-Etsu Chemical Co., Ltd.) X-22-3710)

[Preparation of Treatment Agent 1] In a three-necked flask in which a stirrer and a thermometer were set,
(A) 51.0 g, (b) 190.5 g, (f) 56.
3 g, 6020.0 g of 2-propanol and 14500.0 g of t-butyl alcohol were added and stirred for 1 hour, and then 22.2 g of magnesium perchlorate was added and stirred well. While maintaining the temperature of the solution at 5 ° C. or lower, 67.4 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After dropping, the liquid temperature is 25 ° C
The stirring was continued for five days and nights while maintaining the temperature to obtain a treating agent 1.

[Preparation of Treatment Agent 2] In a three-necked flask in which a stirrer and a thermometer were set,
(A) 45.0 g, (b) 180.5 g, (f) 46.
3 g, (k) 36.1 g, (n) 6.3 g, 2-propanol 6050.0 g, t-butyl alcohol 1500
0.0 g was added and stirred for 1 hour, and then 25.2 g of magnesium perchlorate was added and stirred well. The temperature of this solution is 5
While maintaining the temperature at not higher than 7 ° C., 70.4 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After the completion of dropping, maintain the liquid temperature at 25 ° C.
Stirring was continued day and night to obtain a treating agent 2.

[Preparation of Treatment Agent 3] In a three-necked flask in which a stirrer and a thermometer were set,
(A) 50.0 g, (b) 182.5 g, (f) 50.
3 g, (g) 25.1 g, (k) 40.3 g, 2-propanol 5980.0 g, t-butyl alcohol 155
00.0 g was added and the mixture was stirred for 1 hour. Next, 23.4 g of magnesium perchlorate was added and stirred well. While maintaining the temperature of this solution at 5 ° C. or lower, 74.2 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After the completion of the dropwise addition, stirring was continued for 5 days and night while maintaining the liquid temperature at 25 ° C. to obtain a treating agent 3.

[Preparation of Treatment Agent 4] In a three-necked flask in which a stirrer and a thermometer were set,
(C) 75.5 g and 2425.0 g of ethyl acetate were added,
Stirring was continued for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent 4.

[Preparation of Treatment Agent 5] In a three-necked flask in which a stirrer and a thermometer were set,
(H) 50.0 g, (j) 15.0 g, (e) 10.2
g, ethyl acetate 1911.0 g, toluene 535.4 g
Was added, and the solution was stirred for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent 5.

[Preparation of treating agent 6] In a three-necked flask in which a stirrer and a thermometer were set,
(I) 65.4 g, (d) 5.0 g, (l) 3.2 g,
1900.0 g of isobutyl acetate, methyl ethyl ketone 5
00.0 g was added, and stirring was continued for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent 6.

[Preparation of Treatment Agent 7] In a three-necked flask in which a stirrer and a thermometer were set,
(C) 35.1 g, (I) 35.4 g, (m) 3.5
g and isobutyl acetate (2410.0 g) were added, and the solution was stirred for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent 7.

[Preparation of treating agent 8] In a three-necked flask in which a stirrer and a thermometer were set,
(E) 55.5 g and 2775.6 g of isobutyl acetate were added, and stirring was continued for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent 8.

[Preparation of treating agent 9] In a three-necked flask in which a stirrer and a thermometer were set,
(E) 35.7 g, (d) 24.3 g, ethyl acetate 27
75.6 g was added, and stirring was continued for 24 hours while maintaining the liquid temperature of the solution at 25 ° C. to obtain a treating agent 9.

Example 1 A glass plate of 10 cm × 10 cm (thickness: 3 mm) was pulled up at a rate of 5 cm / min with a solution of the treating agent 8 and dried at room temperature. This test piece was immersed in the solution of the treating agent 1, and the
The sample was pulled up at a different speed and heated at 200 ° C. for 30 minutes to prepare a sample test piece. Table 1 shows the results of evaluating the test pieces.

Example 2 A test and evaluation were conducted in the same manner as in Example 1 except that the treating agent 8 in Example 1 was changed to the treating agent 9. The results are also shown in Table 1.
Shown in

Example 3 A test and evaluation were performed in the same manner as in Example 1 except that the treating agent 1 in Example 1 was changed to the treating agent 2. The results are also shown in Table 1.
Shown in

Example 4 A test and evaluation were conducted in the same manner as in Example 1 except that the treating agent 1 in Example 1 was changed to the treating agent 3. The results are also shown in Table 1.
Shown in

Example 5 A glass plate of 10 cm × 10 cm (thickness: 3 mm) was pulled up at a rate of 5 cm / min with a solution of the treating agent 8 and dried at room temperature. This test piece was immersed in the solution of the treatment agent 4 and was
The sample was pulled up at a different speed and dried at room temperature to prepare a sample test piece. Table 1 shows the results of evaluating the test pieces.

Reference Example 1 A test and evaluation were performed in the same manner as in Example 1 except that the treating agent 4 in Example 5 was changed to the treating agent 5. The results are also shown in Table 1.
Shown in

[0116]

Example 8 A test and evaluation were conducted in the same manner as in Example 1 except that the treating agent 4 in Example 5 was changed to the treating agent 7. The results are also shown in Table 1.
Shown in

Comparative Example 1 A glass plate having a size of 10 cm × 10 cm (thickness: 3 mm) was immersed in the solution of the treating agent 1 and pulled up at a speed of 5 cm / min.
The sample was heated at 200 ° C. for 30 minutes to prepare a sample test piece. Table 1 shows the results of evaluating the test pieces.

Comparative Example 2 A glass plate of 10 cm × 10 cm (thickness: 3 mm) was immersed in a solution of the treating agent 5 and pulled up at a speed of 5 cm / min.
The sample was dried at room temperature to prepare a sample test piece. Table 1 shows the results of evaluating the test pieces.

Comparative Example 3 A glass plate having a size of 10 cm × 10 cm (thickness: 3 mm) was immersed in a solution of the treating agent 8 and pulled up at a speed of 5 cm / min.
The sample was dried at room temperature to prepare a sample test piece. Table 1 shows the results of evaluating the test pieces.

[0121]

[Table 1]

Example 9 The test piece prepared in Example 5 was immersed in the chemicals shown in Table 2 for 24 hours, taken out and washed immediately, and the change in appearance and the removability of water droplets of this test piece were confirmed. Table 2 shows the results.

[0123]

[Table 2]

Example 10 The test piece prepared in Example 1 was immersed in the chemicals shown in Table 3 for 24 hours, taken out and washed immediately, and then the appearance change and the water droplet removability of this test piece were confirmed. Table 3 shows the results.

[0125]

[Table 3]

Example 11 A coating was formed on the surface of a front laminated glass for an automobile by the method of Example 5. The obtained front laminated glass was mounted on the front of a car. The automobile was subjected to a running test for four hours during the day 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.

As a result, generation of dirt, dust, and scale due to the adhesion of water droplets was not observed at all, and even if such generation was recognized in rare cases, it was easily removed by gently wiping with tissue paper. Also, in rainy weather, water droplets on the surface were repelled and moved promptly due to interaction with wind pressure caused by traveling, so that the field of view was secured without using a wiper. Further, in an environment where water droplets adhering to the untreated front laminated glass freeze or the moisture in the air condenses and freezes on the windshield (0 ° C.
In a running test at -5 ° C), no icing on the windshield was observed.

Next, under a more severe low temperature environment (-10 ° C.
At −15 ° C.), icing on the windshield was observed, but the thawing was fast and there was a marked difference compared to the untreated windshield.

Example 12 A running test was conducted by changing the front laminated glass of Example 11 to side glass and rear glass. The same effect as in Example 11 was confirmed.

Example 13 A running test was performed by changing the front laminated glass of Example 11 to a side mirror. The same effect as in Example 11 was confirmed.

Example 14 A front laminated glass of a car, which has been used for 5 years, was polished with calcium carbonate, washed with water, and dried for 1 hour. The treatment agent 9 was spread on the washed front laminated glass with a cotton cloth. After drying for 10 minutes, treatment 4 was spread with a cotton cloth and dried for 10 minutes. Example 1 using this car
A running test similar to that of Example 1 was performed, but the same effect as in Example 12 was confirmed.

Example 15 A coating was formed on the surface of an architectural window glass by the method of Example 5. The window glass thus obtained was attached to 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.

[0133] As a result, no generation of dirt, dust and adhesion of water droplets due to adhesion of water droplets was observed at all, and even if such generation was recognized in rare cases, it was easily removed by gently wiping with tissue paper. In addition, in rainy weather, water droplets on the surface were repelled and fell, and especially on a windy day, the water quickly moved due to the interaction with the wind pressure, and the field of view was secured. Further, in a test (0 ° C. to −5 ° C.) in an environment where water droplets attached to an untreated window glass freeze or water in the air condenses and freezes on the window glass, the temperature of the window glass is reduced. No freezing was seen.

Then, under a more severe low temperature environment (-10 ° C.
At −15 ° C.), icing on the window glass was also observed, but the thawing was fast and there was a marked difference compared to the untreated window glass.

[0135]

The substrate of the present invention or the article provided with the substrate has excellent effects as is clear from the examples.
That is, 1. Excellent in removing water droplets, free of dust, dirt, water droplets, and scales caused by water droplets. In rare cases, they can be easily removed and block the adverse effects of water. In addition, cleaning can be simplified. 2. It has excellent durability of removing water droplets and maintains its state semipermanently.

[0136] 3. It has excellent chemical resistance and can be used along the coastline or in areas where seawater is in direct contact, and can be used in a wide range of fields. 4. No special pretreatment is required, and the economic effect is high. In particular, the durability of water droplet removal is high even at room temperature treatment. 5. The water droplet removal property is optimal for the transportation equipment field and the construction / building equipment field.

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

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-40254 (JP, A) JP-A-63-61057 (JP, A) JP-A-61-10043 (JP, A) JP-A-4- 325446 (JP, A) JP-A-4-288349 (JP, A) JP-A-60-231442 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35 / 00 C03C 15/00-23/00

Claims (5)

(57) [Claims] 1. A surface-treated substrate having at least two surface treatment layers, wherein a first layer, which is the outermost layer of the surface treatment layers, forms a surface having a contact angle value with water of 70 ° or more. the following compounds which may be a layer obtained by treatment with (I), second layer polyfluoro organic is a lower layer in contact with the outermost layer
A surface-treated substrate, which is a layer obtained by treating with an isocyanate silane compound (II) having no organic group. Compound (I): an isocyanate group or a hydrolyzable group
Having at least one bonded silicon atom,
Reactive silane having at least one polyfluoro organic group
Compound. 2. A reactive silane compound, wherein the compound (I) is a reactive silane compound represented by the following formula (A) or (B), wherein at least one of its organic groups is a polyfluoro organic group: The substrate according to claim 1, which is: (A) (Z) _3-ab (R ¹ ) _a (R ² ) _b SI-Y-SI (R ³ ) _c (R ⁴ ) _d (Z) _3-cd where R ¹ , R ² , R ³ , R ⁴ are each independently a hydrogen atom or an organic group having 1 to 21 carbon atoms, Y is a divalent organic group, Z
Is an isocyanate group or a hydrolysable group, a and b are each independently 0, 1 or 2, and an integer satisfying 0 ≦ a + b ≦ 2, and c and d are each independently 0, 1 or 2 and 0 Represents an integer satisfying ≦ c + d ≦ 2. (B) (R ⁵ ) _e (R ⁶ ) _g (R ⁷ ) _h SI (Z) _4-egh , wherein R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or an organic group having 1 to 21 carbon atoms. (However, at least one is an organic group), Z is an isocyanate group or a hydrolyzable group, and e, g, and h are each independently 0, 1, or 2, and represent an integer satisfying 1 ≦ e + g + h ≦ 3. 3. The isocyanate silane compound (II) having no polyfluoro organic group is an organic compound having at least one silicon atom to which 1 to 3 isocyanate groups are bonded, or tetraisocyanate silane. a substrate according to claim 1 or 2. 4. The isocyanate silane compound (II) having no polyfluoro organic group is tetraisocyanate silane or a reactive silane compound represented by the following formula (A) or (B): The substrate according to claim 1 , wherein at least one of Z is an isocyanate silane compound having an isocyanate group. (A) (Z) _3-ab (R ¹ ) _a (R ² ) _b SI-Y-SI (R ³ ) _c (R ⁴ ) _d (Z) _3-cd where R ¹ , R ² , R ³ , R ⁴ are each independently a hydrogen atom or an organic group having 1 to 21 carbon atoms, Y is a divalent organic group, Z
Is an isocyanate group or a hydrolysable group, a and b are each independently 0, 1 or 2, and an integer satisfying 0 ≦ a + b ≦ 2, and c and d are each independently 0, 1 or 2 and 0 Represents an integer satisfying ≦ c + d ≦ 2. (B) (R ⁵ ) _e (R ⁶ ) _g (R ⁷ ) _h SI (Z) _4-egh , wherein R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or an organic group having 1 to 21 carbon atoms. (However, at least one is an organic group), Z is an isocyanate group or a hydrolyzable group, and e, g, and h are each independently 0, 1, or 2, and represent an integer satisfying 1 ≦ e + g + h ≦ 3. 5. The first layer is a layer obtained by treating with a composition containing the compound (I) and an organopolysiloxane.
The substrate according to claim 1 , 2, 3, or 4 .