JP3181310B2 - Surface treatment agent for transportation equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention
Or deposited removal of water droplets directed to a surface treatment agent of the transportation equipment article having easy surface.

[0002]

2. Description of the Related Art In transportation equipment such as trains, automobiles, ships, and aircraft, the surface of articles such as exterior members such as outer plates, windowpanes, mirrors, display device surface materials, and interior members such as instrument panel surface materials. Is preferably always clean. For example, when raindrops, dust, dirt, and the like adhere to the surface of a transport equipment article, or when moisture condenses due to the influence of the temperature and humidity in the atmosphere, there is a problem that its appearance is impaired. If the surface of the transport equipment article is a surface that is directly in contact with human eyes or a surface that is in contact with humans, discomfort and hygiene problems also occur.

[0003] Furthermore, there is a problem that the original function of the surface of the article for transport equipment is remarkably deteriorated, and the article for transport equipment is an article (eg, window glass, mirror, etc.) which requires transparency and visibility. In such a case, the original purpose of the article can not be achieved.

[0004] Means for removing water droplets or the like (for example, removal by wiping or a wiper) may cause minute scratches on the surface. In addition, there is a problem that damage is remarkable due to foreign particles accompanying water droplets or the like. Further, it is well known that when moisture adheres to the glass surface, the glass component elutes in the moisture and the surface is eroded to cause so-called burning. If strong friction is applied to remove this burn, fine irregularities are likely to occur. Glass and the burnt occurs vigorously, perspective field unit of glass produced fine irregularities on the surface, reduces the inherent functions, also are arising disadvantages in terms of scattering is intense field secure light at the surface there is a problem.

[0005] In addition, moisture has a detrimental effect on the surface of transport equipment articles, and promotes damage, contamination, coloring, corrosion, etc., and the electrical, mechanical, and mechanical properties of transport equipment articles.
It may induce changes in optical properties and the like.

In order to solve such a problem, a property of reducing the adhesion of water droplets to the surface of an article for transportation equipment or a property of facilitating the removal of the attached water droplets (hereinafter, these properties are simply referred to as water droplet removing properties) are provided. Is required. Conventionally, as a surface treatment agent for making the surface water-removable, a silicone wax composed of silicone-based wax or organopolysiloxane, a surfactant or the like has been proposed.

[0007] However, the conventional surface treatment agent requires a pre-treatment accompanying the coating, and has a problem that coating unevenness is apt to occur during the coating. Moreover, not be sustained adhesion is low this Toka et surface treatment agent to the substrate, the water drop removal property to a prolonged, yet coverage of the surface treatment agent has been limited.

In addition, it is necessary to take measures against not only the transport equipment articles to be manufactured in the future but also the transport equipment articles already used in consideration of the adverse effect of moisture. It is necessary to impart water droplet removability to already used transport equipment articles only by directly treating them at room temperature. For example, when treating a windshield for an automobile that is already on the market, it is not economical to replace the windshield of the automobile, and it is practically impossible to fire only the windshield after coating. is there. From this viewpoint, there is a problem that conventional surface treatment agents are difficult to cope with.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems. That is, the present inventor:
Study treatment agent capable of eliminating the drawbacks conventional surface treatment agent has, in the course of the study, it can be applied to many types of substrates,
We have found a treatment agent that exhibits excellent water droplet removal properties, and confirmed that various substrates treated with the treatment agent are extremely suitable as substrates having water droplet removal characteristics, particularly as articles for transportation equipment. The invention has been completed. The present invention has a waterdrop removal property, abrasion resistance, chemical resistance, it is excellent in weather resistance, the effect is for the sole purpose of providing a surface treatment agent of the permanently sustainable transport equipment product article.

[0010]

Means for Solving the Problems] The present invention has the following
A composition comprising an isocyanate silane compound represented by the formula (A) or the following formula (B) , or a surface treatment agent for an article for transportation equipment , comprising a composition containing the compound and a solvent: > Offer. (A) (OCN) _3-ab (R ¹ ) _a (R ² ) _b Si-Y-Si (R ³ ) _c (R ⁴ ) _d (NCO) _3-cd where R ¹ , R ² , R ³ and R ⁴ are independently a hydrogen atom
Or an organic group having 1 to 16 carbon atoms, wherein a and b are
0, 1, or 2 and 0 ≦ a + b ≦ 2
And c and d are independently 0, 1, or 2 and
0 ≦ c + d ≦ 2, and Y is a divalent organic group. However
And Y is a divalent organic group having two or more fluorine atoms.
Or at least ^one of R ¹ , R ² , R ³ , and R ⁴
One is an organic group having a polyfluoroalkyl group. (B) (R ⁵ ) _e (R ⁶ ) _g (R ⁷ ) _h Si (NCO) _4-egh wherein R ⁵ , R ⁶ and R ⁷ are independently a hydrogen atom or
Is an organic group having 1 to 16 carbon atoms, and e, g, and h are
Independently, 0, 1, 2, or 3 and 0 ≦ e + g +
h ≦ 3. However, least of R ^5, R ^6, and R ⁷
One is an organic group having a polyfluoroalkyl group
You.

In the present invention, the isocyanate silane compound refers to a compound having a structure in which at least one isocyanate group is directly bonded to a silicon atom. This compound has at least one organic group, and an organoisocyanate having at least one organic group bonded to a silicon atom (the organic group and the silicon atom are bonded by a bond between a carbon atom and a silicon atom). It is a silane compound.

[0012] The surface treated with an isocyanate silane compound, an isocyanate silane compound chemically or <br/> refers to physically bound surfaces. Because the isocyanate groups are reactive, it is believed that the isocyanate silane compound binds to the surface primarily through a chemical reaction.
Chi words, in the coupled state is considered to have the isocyanate groups will vary. For example, it is believed that isocyanate groups react with silanol groups on the glass surface.

In the present invention, at least a part of the properties of the treated surface, such as water drop removability, abrasion resistance, chemical resistance, and weather resistance, is attributable to the reactivity of the isocyanate group, and the other part is attributable to the reactivity. This is considered to be due to the silicon atom directly bonded to the isocyanate group. Further, as described later, by selecting an organic group of the organoisocyanate silane compound, these properties can be further improved. Further, from the viewpoint of the bonding property to the base material, it is more preferable that the number of isocyanate groups bonded to one silicon atom is two or more.

The article for transportation equipment in the present invention includes an outer plate of transportation equipment such as a train, an automobile, a ship, and an aircraft.
Exterior materials such as window glass, mirrors, or display device surface materials,
Parts and components used in transportation equipment such as interior members such as instrument panel surface materials, and parts and components 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 in which a glass mirror is incorporated.

[0015] The type of the substrate of the article for transport equipment is not particularly limited. For example, there are inorganic materials and organic materials such as metals, plastics, glass, and ceramics, and combinations thereof (composite materials, laminated materials, and the like). The surface of the substrate is different from the may be a surface of the substrate itself, a substrate present on the substrate surface such as the surface of the surface treated layer of the coating film surface and surface-treated glass, such as painted metal plate material Surface. In addition, the shape of the base material may be any shape according to the purpose, such as a flat plate, an entire surface or a portion having a curvature.

The substrate in the present invention is preferably a substrate made of a transparent material such as glass or transparent plastic.
As the article for transport equipment in the present invention, an article utilizing the transparency of a transparent material is preferable. Examples of the article include window materials, mirrors, instrument panel protective covers, and the like made of glass, transparent plastic, and the like. These are likely to cause a decrease in the field of view due to the attachment of raindrops, dust, dirt, and the like, which may cause a problem. Glass is particularly preferred as the substrate. It is considered that the isocyanate silane compound reacts with the silanol group of the glass and binds firmly to the surface thereof, and it is considered that even the silicon atom portion binds to the glass surface.

The surface treatment of the substrate is usually carried out by applying an isocyanate silane compound or a composition containing the same to the surface and binding the isocyanate silane compound to the surface. The composition is preferably a solution containing a solvent. Other components can be present in the solution. Other components include, for example, organopolysiloxanes and acids as described below. It is considered that the isocyanate silane compound is brought into contact with the surface of the base material by the application to the base material surface or the subsequent evaporation of the solvent, so that bonding occurs.

The thickness of the surface treatment layer formed by this surface treatment is not particularly limited, but is preferably extremely thin. A preferred layer thickness is 2 μm or less.
The lower limit is the monolayer thickness. One feature of the present invention is that surface treatment does not require particularly high temperatures. That is, the treatment can be performed at room temperature, and it is not necessary to increase the temperature to a temperature required for removing the solvent. Of course, if necessary, the temperature may be raised as long as the effect of the treatment is not lost.

[0019] The isocyanate silane compound is a compound having one or two silicon atoms isocyanate group is bonded. Lee Socia sulfonate silane compound in the present invention include compounds represented by the following formula (A ') or the following formula (B'). Incidentally, 'compound a compound represented by (A Formula (A)' in the following) and good, the formula (B ')
The compound represented by is also referred to as a compound ( B ' ). Also,
A compound represented by the formula (A) or a compound represented by the formula (B)
Are described in the same manner.

( A ′ ) (OCN) _3-ab (R ¹ ) _a (R ² ) _b Si-Y-Si (R ³ ) _c (R ⁴ ) _d (NCO) _3-cd where R ¹ , R ^2, R ^3, and R ⁴ is independently a hydrogen atom or an organic group having 1 to 16 carbon atoms, a and b are independently 0, 1 or 2 and 0 ≦ a + b ≦ 2 der
Ri, c and d are independently 0, 1 or and and a 0 ≦ c + d ≦ 2 2 , Y is a divalent organic group.

( B ′ ) (R ⁵ ) _e (R ⁶ ) _g (R ⁷ ) _h Si (NCO) _4-egh wherein R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a carbon atom. a 1-16 organic group, e, g, and h are independently 0, 1, 2 or 3, and 0 ≦ e + g +
a h ≦ 3.

The compound ( A ' ) is a compound having two silicon atoms bonded to an isocyanate group, and the compound ( B' ) is a compound having one silicon atom bonded to an isocyanate group.
Compound. The compound ( A ' ) is one kind of the organoisocyanate silane compound because Y is an organic group, and the compound ( B' ) is one kind of the organoisocyanate silane compound because it has at least one organic group. . R ^{1 to} R ⁷ are preferably organic groups, and in particular, all R ^{1 to} R ⁷ present are preferably organic groups.

In the compound ( A ' ) and the compound ( B' ), the number of isocyanate groups bonded to silicon atoms is preferably two or more per silicon atom. This is because the more isocyanate groups, the stronger the bond to the substrate surface.

Compound (A ') and compound (B')
When R ^{1 to} R ⁷ are an organic group, the organic group includes a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, a chloroalkyl group, or a polyfluoroalkyl group. Has a functional group such as a halogenated hydrocarbon group, hydroxyl group, epoxy group, amino group, mercapto group, or carboxyl group (halogenation)
Preferred are hydrocarbon groups and (halogenated) hydrocarbon groups having a linkage such as an ester bond, an ether bond, a thioether bond, an imino bond, or an amide bond in the middle of the carbon chain. Particularly preferred is an organic group having a hydrocarbon group and a polyfluoroalkyl group. Preferred hydrocarbon groups include alkyl and aryl groups having 1 to 16 carbon atoms.

The isocyanate silane compound is such that Y in the formula ( A ′ ) is an alkylene group and R ¹ ,
A compound in which at least one of R ² , R ³ and R ⁴ is an alkyl group, or a compound in which at least one of R ⁵ , R ⁶ and R ^{7 in} the formula ( B ′ ) is an alkyl group is preferred. In particular, when all of R ^{1 to} R ^{4 in} the compound ( A ′ ) are an alkyl group having 4 or less carbon atoms (hereinafter, referred to as a lower alkyl group), all of R ^{5 to} R ^{7 in} the compound ( B ′ ) Is a lower alkyl group, R ¹ in the compound ( A ′ )
0 to 1 of R ² and R 0 or 0 to 1 of R ³ and R ⁴
Is an alkyl group other than a lower alkyl group and the other is a lower alkyl group, or R ⁵ in the compound ( B ′ )
It is preferred that 0 to 1 of R ⁷ to R ⁷ are an alkyl group other than a lower alkyl group and the others are lower alkyl groups. A particularly preferred lower alkyl group is a methyl group.

The compounds of the present invention (A) and the compound (B) is a organosilane isocyanate silane having two or more fluorine atoms. That is, compound (A),
Y is a divalent organic radical is of having two or more fluorine atoms
And Y is a group other than a divalent organic group having two or more fluorine atoms, and at least one of R ^{1 to} R ⁴ is a polyfuran.
A compound which is a monovalent organic group having an oloalkyl group , or wherein at least one of R ^{1 to} R ⁴ is a polyfluoroalkyl group
In it and Y is a compound which is a divalent organic group having two or more fluorine atoms. Further, compound (B), R ⁵ ~
A compound in which at least one of R ⁷ is a monovalent organic group having a polyfluoroalkyl group .

As the organic group having no fluorine atom in the preferred compound ( A ' ) and compound ( B' ), the above-mentioned hydrocarbon groups are preferred. The compound (A)
The organic group or polyfluoroalkyl group having two or more fluorine atoms in compound (B) is preferably bonded to a silicon atom by a carbon atom having no fluorine atom (eg, a methylene group).

The reduction compound (A), the Y is a divalent organic group having two or more fluorine atoms, as the base polyfluoroalkylene group, polyfluoro oxaalkylene group (the carbon chain of the alkylene group Preference is given to those having at least one ether bond in the middle) and polyfluorothiaalkylene groups (having at least one thioether bond in the middle of the carbon chain of the alkylene group). In particular, a divalent organic group in which the moieties bonded to silicon atoms at both ends are polymethylene groups (particularly dimethylene groups), and the intermediate portion thereof is a perfluoroalkylene group, perfluorooxaalkylene group, or perfluorothiaalkylene group Is preferred. These Y have 6 to 3 carbon atoms.
0 is preferable, and especially 6 to 16 is preferable.

[0029] In have you to Compound (A), in the case where Y is a divalent organic group other than the group having two or more fluorine atoms, as the base alkylene, oxaalkylene group or thiaalkylene group, is preferable. The carbon number is preferably from 2 to 30, particularly preferably from 2 to 16.

Compound (A) and Compound (B)
Te, any one of R ¹ to R ⁷ may be a monovalent organic group having a polyfluoroalkyl group, as this group polyfluoroalkyl group, polyfluorooxaalkyl group, polyfluoroalkyl thia alkyl group, or a mixture, And the group
An organic group in which a hydrocarbon group such as an alkylene group is bonded by an ester bond or the above-described linking bond (however, a silicon atom is bonded to the other end of the hydrocarbon group) is preferable. In particular,
A group in which the end bonded to the silicon atom of the perfluoroalkyl group, perfluorooxaalkyl group, or perfluorothiaalkyl group or its periphery is an alkylene group (particularly, a dimethylene group is preferable) is preferable.

When the monovalent organic group has a perfluoro moiety, the moiety is preferably a perfluoroalkyl group having 3 or more carbon atoms, a perfluorooxaalkyl group, or a perfluorothiaalkyl group, particularly preferably having 3 to 16 carbon atoms. Are preferred.

For specific examples of Y and R ^{1 to} R ⁷ ,
Examples of the specific examples of the following compound ( A ' ) and compound ( B' ) are given. R _f in the following specific examples is C _n F
_{2n + 1 C m H 2m -} ( where, n is an integer of 3 to 16, m is 2
An integer from 4 to 4. )), A polyfluoroalkyl group having a perfluoroalkyl group moiety is preferable, and R _F in the following specific examples is C _n F _{2n + 1-} (where n is 3 to
An integer of 16. Is preferred.

Specific examples of the compound ( A ' ) and the compound ( B' ) are shown below. However, the compound ( A ' ) and the compound ( B' ) are not limited to these specific examples. In the following chemical formulas, x, n, and m each represent an integer of 1 or more,
R represents an alkyl group or the like; R _f represents a polyfluoroalkyl group; R _F represents a perfluoroalkyl group;
However, R is preferably a lower alkyl group, and R _f is preferably a dimethylene group having a perfluoroalkyl group. In the present invention
As the compound (A) and the compound (B), the following specific examples
Wherein Y in compound (A ') is two or more
Compound which is a divalent organic group having an atom, compound (A ′)
In which at least one of R ¹ , R ² , R ³ and R ⁴ is
A compound that is an organic group having a polyfluoroalkyl group,
R ⁵ or the compound (B '), R ^6, and R ⁷
Organic having at least one polyfluoroalkyl group
The compound that is the group is selected.

Illustrative of compound ( A ' ).

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

[0044]

Illustrative of compound ( B ' ).

[0046]

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[0047]

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[0048]

Further, in the present invention, in order to enhance the effect of the surface treatment with the isocyanate silane compound, it is preferable to use an organopolysiloxane together with the isocyanate silane compound. As the organopolysiloxane, those called silicone oil or modified silicone oil are suitable. Hereinafter, this organopolysiloxane is also referred to as compound (C). The compound (C) preferably has a polymerized unit represented by the following formula (C).

(C) [—SiX (CH ₃ ) —O—] wherein X represents an organic group having 1 to 16 carbon atoms. The organic group is preferably the same organic group as R ^{1 to} R ⁷ (however, those having no fluorine atom are preferable), and particularly, an alkyl group, an aryl group, an arylalkyl group, an aminoalkyl group, a hydroxyalkyl group Or a hydrocarbon group having a polyoxyalkylene chain, particularly a lower alkyl group.

The compound (C) has an effect of improving the water droplet removal property and the abrasion resistance of the coating by the treatment with the isocyanate silane. This compound (C) preferably does not have a hydrolyzable group. The compound (C) may be used in the composition for surface treatment as it is, or may be added to the composition after being decomposed with an acid such as sulfuric acid, hydrochloric acid, or acetic acid.
I can . The kinematic viscosity of the compound (C) is as follows:
It is preferable to determine in consideration of the combination with the compound (B), and it is particularly preferable that the kinematic viscosity at 25 ° C. is 0.5 to 500 centistokes (cSt).

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

[0053]

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[0054]

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The compositions for surface treatment in the present invention shall be the essential compound (A) or compound either a compound of (B). Of course, there is no problem even if both compounds are contained, and the ratio may be arbitrary. Compound (C)
When components are added, the ratio of compound (C) to compound (A) and / or compound (B) can be arbitrarily determined according to the purpose. Preferably, compound (A),
It is preferable that the amount of the compound (C) or a decomposition product thereof is 1 to 40% by weight based on the total of (B) and (C).
If the amount of the compound (C) is too small, the abrasion resistance and workability are likely to be reduced. If the amount of the compound (C) is too large, not only the abrasion resistance is reduced, but also a sticky feeling may be left when touching the surface.

Further, the compound (C) contributes to the improvement of the water-removability of the film and the durability of the film by interaction with the compound (A) and / or the compound (B). Although the detailed mechanism is unknown, the molecular chain of compound (C) is
Compound (A) and compound (B) are intricately entangled with the compound,
Various organic groups present on the surface, especially consequently control the microscopic distribution of polar groups and ionic bond, with the idea we are Ru because optimal surface structure for the removal of water droplets is achieved.

It is considered that the entanglement of molecules between the selected compounds greatly contributes to further increasing the durability. Compounds (A), (B) and (C) are all substances having a low surface free energy, and the free compound partially present in the coating film moves on the very surface layer to cause friction on the surface. It is also considered that reducing the resistance is one of the causes of good wear resistance.

Other compounds and additives are added to the surface treating agent of the present invention according to the purpose. Additive reactive with the components, ultrafine particles may various metal oxide be selected in consideration of compatibility, various resins Ru can be added. If coloring is necessary, a dye, a pigment or the like may be added. These additives are a total of 10 of the compounds (A), (B) and (C).
0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, based on 0 parts by weight. Excessive addition is undesirable because it reduces the water drop removal properties and abrasion resistance of the present invention.

[0059] The composition may be applied by the method of hand wiping or the like directly to the substrate to be coated and by the organic solvent, dissolving or diluting prepared solution form of Ru can also be used . In the solution using the organic solvent, the total amount of the compounds (A), (B), and (C) contained is determined in consideration of the film formability (workability), stability, film thickness, and economy. Is preferably 0.1 to 30% by weight.

[0060] acid esters as organic solvent, aromatic hydrocarbons, halogenated hydrocarbons, ketones, and Ru can be employed various solvents such as ethers, and has a reactive functional group (such as a hydroxyl group) Is compound (A) or compound (B)
It is not desirable because it reacts with the isocyanate group contained in the component. However, an organic solvent having a functional group having low reactivity such as isopropyl alcohol can be used. Diluting solvent is not limited to one, Ru can also be used in combination of two or more solvents.

In the treatment, no special pretreatment is required, but it is not particularly problematic to carry out the treatment according to the purpose. For example, acid treatment with diluted hydrofluoric acid, hydrochloric acid, etc., alkali treatment with sodium hydroxide, potassium hydroxide aqueous solution, etc. Treatment or discharge treatment by plasma irradiation or the like can be performed.

The coating 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, brush coating, flow coating, spin coating, dip coating, spray coating, etc. performed by a method, the atmosphere or nitrogen Motochu may be dried at room temperature. However, there is no problem in heating for the purpose of increasing the drying speed. When heating, the temperature and time may be set in consideration of the heat resistance of the substrate.

The thickness of the film to be formed can be appropriately controlled by the composition concentration of the liquid containing the composition, application conditions, heating conditions and the like. Due to the relatively low refractive index of the coating according to the invention, low reflectivity is also provided. If such an effect is expected, the film thickness of the film may be controlled to a value 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 the water droplet removal property, and it is desirable that the film thickness be 2 μm or less as described above in consideration of the economic effect.

[0064] The substrate having such a coating Ru can be easily mounted or as part thereof as an article for transportation equipment. For example, the body of a train, window glass, pantograph, etc., the body of an automobile (truck), windshield, rear glass, side glass, mirror, bumper, etc., the body of a ship, the window glass, the body of an aircraft, the window glass, etc. you can use.

In the surface-treated substrate, water droplets adhering to the surface are repelled by the water droplet removing property, and particularly, the water droplets rapidly move on the surface due to the interaction with the wind pressure received during operation and collect as water droplets. no, Ru can eliminate the adverse effects of moisture-induced. In particular, when the base material is used in a transparent field of view such as a window glass, it becomes very easy to secure a visual field due to scattering of water droplets.

Further, even in an environment where water droplets freeze, freezing does not occur, and thawing is extremely rapid even if the water freezes. 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 maintaining aesthetic appearance.

[0067]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to the examples. Various evaluations in the examples were performed by the following methods.

1. Water Drop Removability (1) The falling angle of a water drop having a diameter of 2 mm was measured. The measurement was performed at five different locations on the surface, and the average value was shown. (2) Water was sprayed over the entire surface for about 1 hour from a nozzle held at a distance of 20 cm from the sample surface, and then 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: Significant water droplets remain on the sample surface. D: Water spreads on the sample surface.

2. Abrasion resistance Testing machine: Taber type rotary abraser (Toyo Seiki Seisaku-sho, Ltd.) Test conditions: Wear wheel H-22, load 1kg, wear frequency 30
0 times. After the abrasion resistance test was carried out by the above method, the water droplet removability 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 the water drop removal property after 100 cycles was evaluated.

4. Boiling test The water drop removal property after immersion in boiling water for 1 hour was evaluated.

5. Compound b1: C ₈ H ₁₇ Si (NCO) ₃ b2: CH ₃ Si (NCO) ₃ b3: (CH ₃ ) ₂ Si (NCO) ₂ b4: (CH ₃ ) ₃ SiNCO b5: Si (NCO) ₄

B6: Ph-Si (NCO) ₃ (Ph represents a phenyl group) a1: (OCN) ₃ SiC ₂ H ₄ Si (NCO) ₃ a2: (OCN) ₂ (CH ₃ ) SiC ₂ H _{4 Si (CH 3) (NCO)} 2 b7: C 8 F 17 C 2 H 4 Si (NCO) 3 a3: (OCN) 3 SiC 2 H 4 C 6 F 12 C 2 H 4 Si (NCO) 3

C1 : (CH ₃ ) ₃ SiO— [Si (CH ₃ ) ₂ —O—] _m —Si (CH ₃ ) ₃ (m, n: an integer of 1 or more; kinematic viscosity: 50 cSt) c2: (CH ₃ ) ₃ SiO- [Si (CH ₃ ) ₂ -O-] _m- [Si (CH ₃ ) (C ₃ H ₆ NH ₂ ) -O
-] _n -Si (CH ₃ ) ₃ (m, n: an integer of 1 or more)

[Preparation of Treatment Agent 1] 19.3 g of b1 and 1980.0 g of butyl acetate were added to a flask in which a stirrer and a thermometer were set. After addition of 0.7 g of c1, the temperature of the solution was raised to 25.
Stirring was continued for 24 hours while maintaining the temperature at 0 ° C to obtain a treating agent 1.

[0077] In the treatment agent 2 Preparation] stirrer and a thermometer was set flask, b2 of 15.3 g, 1.1 g of b3, b4 of 0.8 g, were mixed 1.4g of b5, acetic acid 1985.3 g of butyl were added. Furthermore, after adding 0.3 g of c1 and 0.4 g of c2, stirring was continued for 24 hours while maintaining the solution temperature of the solution at 25 ° C. to obtain a treating agent 2.

[Preparation of Treatment Agent 3] In a flask in which a stirrer and a thermometer are set,b1
18.4 g,a110.1 g were mixed and toluene 25
61.3 g were added. furtherc12.1g,c2
After adding 1.3 g, maintain the solution temperature at 25 ° C.
Stirring was continued for one day and night while treating agent 3 was obtained.

[0079] In the treating agent Preparation of 4] stirrer and flask thermometer is set, b1 of 12.1 g, b2 of 5.1 g, b6 of 5.1 g, were mixed 7.8g of a2, toluene 1877.7 g were added.
After further adding 3.2 g of c1 and 0.4 g of sulfuric acid, stirring was continued for 5 days while maintaining the solution temperature at 25 ° C. to obtain a treating agent 4.

[Preparation of treating agent 5] In a flask in which a stirrer and a thermometer were set , 19.9 g of b7 and 10.3 g of a3 were mixed.
85.3 g, 54.2 g of isopropyl alcohol, 456.3 g of Freonsolve (R-113) and 0.7 g of sulfuric acid were added. After further adding 0.7 g of c1, stirring was continued for 5 days while maintaining the solution temperature of the solution at 25 ° C. to obtain a treating agent 5.

[Preparation of Treatment Agent 6] In a flask in which a stirrer and a thermometer are set,b1
9.8 g,b52.3 g,a13.5 g,b7
9.8 g, butyl acetate 985.3 g,
Pill alcohol 33.2 g, Freonsolve (R-11)
3) 200.0 g was added. furtherc1Add 0.8g
After the addition, maintain the solution temperature at 25 ° C. for one day.
Stirring was continued overnight to obtain treating agent 6.

[Preparation of Treatment Agent 7] In a flask in which a stirrer and a thermometer are set,b1
120.0 g,b27.8 g,b53.5 g,a1
of2.4 g, 988.8 g of ethyl acetate, isop
23.5 g of propyl alcohol were added. furtherc1
After adding 4.5 g and 0.7 g of sulfuric acid, the solution temperature
The stirring was continued for 5 days while maintaining the
Obtained.

[0083] To a flask stirring bar and a thermometer was set Preparation of treatment agent 8], b1 of 18.4 g, a 10.1g of a1 were mixed, toluene 25
After the addition of 61.3 g, the solution was continuously stirred for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent 8.

[0084] In the treating agent Preparation of 9] stirrer and a thermometer was set flask filled with isopropyl alcohol 2561.3G, 2 of c1.
After the addition of 1 g and 1.3 g of c2, stirring was continued for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent 9.

Comparative Example 1 A glass plate of 10 cm × 10 cm (thickness: 3 mm) was immersed in a solution of the treating agent 1 and pulled up at a rate of 11 cm / min to prepare a sample test piece. Table 1 shows the results of evaluating the test pieces.

[ Comparative Examples 2 to 6 ] The treating agent 1 in Comparative Example 1 was replaced with treating agents 2 , 3,
Tests and evaluations were performed in the same manner as in Comparative Example 1, except that the test conditions were changed to 4, 7, and 8. Table 1 shows the results. [Examples 1 and 2] The treating agent 1 in Comparative Example 1 was replaced with treating agents 5 and 6, respectively.
The test and evaluation were performed in the same manner as in Comparative Example 1 except for the change. Conclusion
The results are shown in Table 1.

[0087] [Comparative Example 7] the exception that the treating agent 1 in Comparative Example 1 treating agent 9 ratio
Compare Example 1 and similarly tested and evaluated. Table 1 shows the results.

[Example 3 ] The test piece having a film formed thereon obtained in Example 1 was immersed in a chemical shown in Table 2 for 24 hours, taken out and immediately washed, and then the appearance change and water drop of the test piece were measured. Removability was confirmed. Table 2 shows the results.

Example 4 A coating was formed on the surface of a front laminated glass for an automobile by the method of Example 1 . The obtained front laminated glass was mounted on the front of a car. With this car, a running test for four hours during the day was performed for one month, and the state of dirt and dust on the front surface and the state of adhesion of water drops in rainy weather were visually observed every day.

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

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

Example 5 A running test was performed by changing the front laminated glass of Example 4 to side glass and rear glass. The same effect as in Example 4 was confirmed.

Example 6 A running test was performed by changing the front laminated glass of Example 4 to a side mirror, and the same effect as in Example 4 was confirmed.

[Example 7 ] The surface of a front laminated glass for an automobile, which has been used for one year, has been polished with cerium oxide and rinsed with a sufficient amount of water.
Moisture was completely removed with a drier, and water residue, dirt, dust, and the like, which had already accumulated on the surface, were completely removed. Wipe the entire surface of the washed front laminated glass with a cotton cloth impregnated with the treating agent 5 by waxing,
Dried. After drying sufficiently, water was applied to confirm that a film was formed on all surfaces. Thereafter, a test similar to that of Example 4 was performed, and it was confirmed that the water droplet removing property shown in Example 4 was good.

[Example 8 ] The surface of a painted body of an automobile, which has been used for one year, is polished with cerium oxide, rinsed with sufficient water, completely dried with a drier, and is already deposited on the surface. Dust, dirt, dust and the like were completely removed. The entire surface of the washed painted body portion was wiped by hand with a cotton cloth impregnated with the treating agent 5, and dried. After drying sufficiently, water was applied to confirm that a film was formed on all surfaces. Thereafter, a test similar to that of Example 4 was performed, and it was confirmed that the water droplet removing property shown in Example 4 was good.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

EFFECTS OF THE INVENTION As described in the Examples , the present invention has excellent effects on the base material for transport equipment and the articles for transport equipment treated with the surface treatment agent of the present invention and the transport equipment equipped with them. Is recognized. That is, 1. Has excellent water droplet removal property, dust, dirt, water droplets adhesion of, or no such occurrence of fur due to it, Mareni even if their generation, eliminates adverse effects easily removable inducible water In addition, the cleaning can be simplified. 2. It has excellent durability of removing water droplets and maintains its state semipermanently.

3. It has excellent chemical resistance and can be used along the coastline.
for,AlsoIs also effective on ships in direct contact with seawater
I do. 4. No special pretreatment is required, and the economic effect is high. 5. Applicable to transport equipment already in common useCan
You. These effects cannot be expected with conventional materials.
Yes, even in areas where it was previously unusable
The range can be expanded.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09K 3/00 C09K 3/00 112 B60J 1/00-1/20 C03C 17/30

Claims (2)

(57) [Claims] 1. A lower following formula (A) or a composition containing an isocyanate silane compound represented by the following formula (B), or
A product for transportation equipment, comprising a composition containing the compound and a solvent.
Product surface treatment agent. (A) (OCN) _3-ab (R ¹ ) _a (R ² ) _b Si-Y-Si (R ³ ) _c (R ⁴ ) _d (NCO) _3-cd where R ¹ , R ² , R ^3, and R ⁴ is independently a hydrogen atom or an organic group having 1 to 16 carbon atoms, a and b are independently 0, 1 or 2 and 0 ≦ a + b ≦ 2 der
Ri, c and d are independently 0, 1 or and and a 0 ≦ c + d ≦ 2 2 , Y is a divalent organic group. However
And Y is a divalent organic group having two or more fluorine atoms.
Or at least ^one of R ¹ , R ² , R ³ , and R ⁴
One is an organic group having a polyfluoroalkyl group. (B) (R ⁵ ) _e (R ⁶ ) _g (R ⁷ ) _h Si (NCO) _4-egh wherein R ⁵ , R ⁶ and R ⁷ are independently a hydrogen atom or a C 1-16 an organic group, e, g, and h are independently 0, 1, 2 or 3, and 0 ≦ e + g +
a h ≦ 3. However, least of R ^5, R ^6, and R ⁷
One is an organic group having a polyfluoroalkyl group
You. 2. The surface treating agent according to claim 1 , wherein the composition further contains an organopolysiloxane.