JP3212320B2 - Article for transport equipment and method for manufacturing article for transport equipment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a small adhesion of water droplets,
Or transportation equipment article having a removal easy surface water droplets attached, and about the method of manufacturing an article for the transportation equipment
You.

[0002]

BACKGROUND OF THE INVENTION train, to have your automobile, ship or in transportation equipment such as aircraft, outer panel, window glass, mirrors, exterior member such as a display device surface material or the instrument panel surface material and the like of the interior member, and other Preferably, the surface of the article is always clean. An example
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. Transport aircraft
If the surface of the dexterous 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] In addition, there is also a problem of lowering significantly the inherent functions of the transport equipment for the article surface, wherein the transport device for articles in a transparent, articles that require fluoroscopic wild (e.g., window glass or mirrors, etc.) in some cases, can not be achieved the original purpose of the thing goods, there is a possibility that the cause of inducing a serious accident.

[0004] means for removing water drops, etc. (e.g., removal by wiping or wiper) may be given a fine scratches on the front side. Further, the foreign particles are accompanied by water droplets, some damaged wrote Kunar problem. 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. When the friction strongly in order to remove the burnt not ease produce fine irregularities. 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 .

[0005] and other moisture can damage adversely affect the surface of the transport equipment for the goods, pollution, colored, to promote corrosion and electrical properties of the transport equipment for the goods, mechanical properties,
It may induce changes in optical properties and the like.

[0006] To solve such problems, small Kusuru property of adhesion of water droplets to the transport equipment for the surface of the article or (hereinafter referred to simply water droplet removal property) nature to facilitate the removal of water droplets attached of the grant is that not being sought. Then the surface from slave <br/> come as a surface treatment agent to water drop removal property, shea Li <br/> co over emissions system consists wax or an organopolysiloxane sheet <br/> Ricoh down oil, or a surfactant Agents and the like have been proposed.

[0007] However, the conventional surface treatment agent, require pretreatment with the coating, and coating unevenness ease occurs at the time of coating
There was a willing subject. Further, since the low adhesion surface treatment agent to the base material, can not sustain the water droplet removal property to a prolonged, yet coverage of the surface treatment agent has been limited.

[0008] Also, when you take into account the adverse effects of moisture, as well as goods for transportation equipment, which is fabricated future, measures need a lecture Jill even for already goods for transportation equipment that is being used. The transport equipment article that has already been used, it is necessary to apply only in water drop removal property directly treated at normal temperature. For example, Cormorant rows processing <br/> management in automobile windshields which are already commercially available case, replace the windshield of each automobile
This is not economical, and it is not practically possible to fire the windshield after application. From this point of view also correspondence Ru difficult problem Oh <br/> the conventional surface treatment agent.

[0009]

[0008] The present invention has been made in view of the problems and disadvantages of the. That is, the present inventor:
Studies of treatment agent conventional surface treatment agent can eliminate the drawback of chromatic, in the course of study, applicable to many types of substrates are possible, it found processing agent exhibits excellent water droplet removal property,
Moreover, it has been confirmed that various substrates treated with the treating agent are extremely suitable as substrates having a water droplet removing property, particularly as an article for transportation equipment, and have completed the present invention . This onset <br/> Ming has water drop removal property, abrasion resistance, chemical resistance, it is excellent in weather resistance, transportation equipment article whose effect lasts semipermanently, and articles for the transport equipment The purpose of the present invention is to provide a manufacturing method .

[0010]

That is, the present invention relates to a base material
Consisting treated substrate having at least two treated surface layers on the surface, or as a component of the treated substrate, an article for transportation equipment, the first layer is the outermost layer of the surface treatment layer is an isocyanate silane compound is a layer obtained by treating with a treating agent (I), then the second layer is a hydrolyzable silane compound is a lower layer in contact with the outermost layer (II) or treatment agent comprising a partial hydrolysis product Is a layer obtained by processing
Articles for transportation equipment and methods for manufacturing the articles for transportation equipment
Provide .

In the present invention, the isocyanate silane compound (I) refers to a compound having a structure in which at least one isocyanate group is directly bonded to a silicon atom.
This compound may have at least one organic group, or may be a compound having no organic group such as tetraisocyanate silane. Preferably, it is an organoisocyanate silane compound 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 ).

[0012] The isocyanate silane compound (I) in the treated surface, an isocyanate silane compound (I) refers to the surface of the first layer is also chemically physically associated.
Since the isocyanate group is reactive, it is considered that the isocyanate silane compound (I) is bonded to the surface of the second layer mainly by a chemical reaction. Chi words, in the coupled state is considered to have the isocyanate groups will vary. 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.

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. Also as described later, by selecting the organic group of Lee Socia sulfonate silane compound (I), Ru further improve Saseu <br/> these performances. Further, from the viewpoint of the binding property to the surface of the second layer, it is more preferable that the number of isocyanate groups bonded to one silicon atom is two or more.

[0014] The Contact Keru transport equipment for the goods to the present invention, trains, automobiles, ships, outer plate in transportation equipment such as aircraft,
Exterior materials such as window glass, mirrors, or display device surface materials,
Interior members such as the instrument panel surface member, the other used to transportation equipment which parts and components, or refers to parts and components used in transportation equipment. The article may be composed solely processed substrate subjected to surface treatment, or may be surface-treated treated substrate is incorporated. 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 base material of the article for transportation equipment is not particularly limited.
Lena had. For example, metal, plastic, glass, ceramics, other inorganic materials and organic materials, also Re Waso
There are combinations of these (composite materials, laminated materials, etc.). The surface of the substrate, even the surface of the substrate itself, the surface of a coating film such as a painted metal plate or the surface of a surface-treated layer of surface-treated glass
It may be a surface made of a material different from the front surface of the base material itself and the like. Further, the flat plate as the shape of the substrate whole surface,
Or Ru include any shape according to the purpose such as those having a partially curvature.

[0016] as your Keru base material in the present invention, a substrate made of Toru Akirazai fee, such as glass or transparent plastic is preferable.
The article for the transportation equipment of the present invention is preferably an article utilizing the transparency of the transparent material, for example, a window material consisting of glass or transparent plastic, mirrors, instrument panel protective cover or the like
It is Ru and the like. These raindrops, dust, due to the adhesion of dirt, perspective wild is rather ease lowered, its Reniyo Ri problems Ru Ah is a risk of calling <br/> production. Glass is particularly preferred as the substrate. Preferably, the second layer reacts with the silanol groups of the glass and binds strongly to its surface.

In the surface treatment of the surface of the second layer , a treating agent containing an isocyanate silane compound (I ) is usually applied to the surface of the second layer, and the isocyanate silane compound (I ) is applied to the second layer .
Preferably, it is performed by bonding to the layer surface. I
The treating agent containing the soocyanate silane compound (I) is preferably a solution containing a solvent. Other components can be present in the solution. Examples of other components, for example, Ru include organopolysiloxanes and acids as described below. Processing for forming the first layer on the surface of the second layer
By coating or volatilization of the subsequent solvent agent, an isocyanate silane compound (I) is considered to be bonded into contact with the surface of the second layer takes place.

The thickness is particularly LIMITED Lena bur of the first layer to produce by this surface treatment, it is preferable that extremely thin. Preferred thickness of the first layer is less 2.mu. m. The lower limit is the monolayer thickness. One feature of the present invention is that no special high temperatures are required when treating the surface of the second layer. That is, it is possible to perform processing at room temperature, it <br/> need not be temperature or more necessary even when the removal of the solvent. Of course, if necessary, it may be high temperature as long the effect of the treatment is not lost.

[0019] In the isocyanate silane compound (I)
Is preferably a compound having one or two silicon atoms having an isocyanate group bonded thereto. Isocyanate silane compound
(I) may have a silicon atom to which no isocyanate group is bonded. However, the presence of silicon atoms hydrolyzable group is bonded is not rather preferable. Preferred isocyanate silane compounds (I) are represented by the following formula (A)
That compound or a compound represented by the following formula (B). Hereinafter, the compound represented by the formula (A) is also referred to as a compound (A), and the compound represented by the formula (B) is also referred to as a compound (B).

(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 hydrogen
Atom or an organic group having a carbon number of 1 ~ 16, a and b are independently 0, 1 or 2 der Li Kui 0 ≦ a + b ≦ 2 integer that satisfies, c and d are independently 0, 1 or 2, der Ri
And an integer satisfying 0 ≦ c + d ≦ 2, Y represents a 2 Ataiyu machine group.

(B)(R ^Five ) _e (R ⁶ ) _g (R ⁷ ) _h Si (NCO) _4-egh  Where R^Five , R⁶ ,andR⁷ Independently,hydrogenatomMa
Or 1 carbon~16 organic groups, e, g,andh is independent
To,0, 1, 2,Or3Rikatsu0 ≦ e + g + h ≦
Represents an integer satisfying 3.

The compound (A) is a compound having two silicon atoms having an isocyanate group bonded thereto, and the compound (B)
Is a compound having one silicon atom to which an isocyanate group is bonded. In compound (A), whether Y is an organic group
Ri 1 Tanedea Luo organo isocyanate silane compound,
When compound (B) has at least one organic group
In a one organo isocyanate silane compound. R ¹ to R ⁷ are rather is preferably in the range of organic groups, in particular, all R ¹ to R ⁷ which is present is preferably an organic group.

[0023] In compounds (A) and (B), the isocyanate group bonded to a silicon atom or two or Ah silicon atom. This is because the more isocyanate groups, the stronger the bond to the substrate surface.

[0024] When R ¹ to R ⁷ is an organic group, the organic group, an alkyl group, an alkenyl group, a cycloalkyl group or a hydrocarbon group such as an aryl group, chloroalkyl group, or a polyfluoroalkyl group, halogenated hydrocarbon group, a hydroxyl group, an epoxy group, an amino group, a mercapto group or having a functional group such as a carboxyl group (halogenated) hydrocarbon group, the intermediate ester bond charcoal Motokusari, an ether bond, a thioether bond, (Halogenated) hydrocarbon groups having a linking bond such as an imino bond or an amide bond are preferred. Particularly preferred is an organic group having a hydrocarbon group or a polyfluoroalkyl group. preferable
As the hydrocarbon group, an alkyl group having 1 to 16 carbon atoms and an a
A reel group.

As the isocyanate silane compound (I)
Is a compound wherein Y in the formula (A) is an alkylene group,
R ¹ , R ² , R ³ or R ⁴ is present in the formula (A)
Wherein at least one of the compounds is an alkyl group,
When R ⁵ , R ⁶ or R ⁷ is present in the formula (B)
Compounds in which at least one is an alkyl group are preferred
No. In particular, R ¹ to R ⁷ are all alkyl group of 4 or less (hereinafter, referred to as lower alkyl group) carbon or a, R ¹ to R ^2, R ³ to R ⁴ bonded to one silicon atom, also <br/> If other and is an alkyl group other than one of which a lower alkyl group when there are R ⁵ to R ⁷ is a lower alkyl group is preferred. A particularly preferred lower alkyl group is a methyl group.

Further, preferred compounds (A) and (B) is a organosilane isocyanate silane having two or more fluorine atoms. In other words, you in the compound (A)
That Y is 2 Ataiyu machine group of having two or more fluorine atoms
Compound , except that Y is a divalent organic group having 2 or more fluorine atoms
And a divalent organic radical one even without least of R ¹ to R ⁴ is a 1 Ataiyu machine group having 2 or more fluorine atoms compounds of
Or, at least one Y of R ¹ to R ⁴ is a compound Ru organic radical der having two or more fluorine atoms. Compound
In (B), at least one of R ^{5 to} R ⁷ is 2 or more.
A compound that is a monovalent organic group having a fluorine atom,
You.

In the compound (A) and the compound (B ), when an organic group having no fluorine atom is present ,
The aforementioned hydrocarbon groups are preferred. Incidentally, the organic group having two or more fluorine atoms, carbon atoms having no full Tsu atom (e.g., methylene group) is preferably bonded to a silicon atom in.

[0028] In preferred compounds (A), in the case where Y is 2 Ataiyu machine group having 2 or more fluorine atoms, and the substrate
To the polyfluoroalkylene group, polyfluoro oxaalkylene group (those that there is at least one ether linkage in the middle of the carbon chain of the alkylene group), and Porifuruorochi A alkylene group (at least one in the middle of the carbon chain of the alkylene group With a thioether bond)
Is preferred. In particular, the portion bonded to the silicon atoms at both ends is a polymethylene group (particularly dimethylene group), their middle portion perfluoroalkylene group, perfluoro oxaalkylene group, or in Pafuruorochi A alkylene <br/> emissions group there 2 Ataiyu machine group. The carbon number of Y is preferably from 6 to 30, particularly preferably from 6 to 16.

[0029] When Y in the compound (A) is a group other than 2 Ataiyu machine group having 2 or more fluorine atoms, and the base
Alkylene group Te, oxaalkylene group or Chi A A <br/> alkylene group, is preferable. Its carbon number is preferably 2-30
And particularly preferably 2 to 16.

[0030] When any of R ¹ to R ⁷ is 1 Ataiyu machine group having 2 or more fluorine atoms, as the base polyfluoroalkyl group, polyfluorooxaalkyl group, Porifuruorochi A alkyl group or they, or a group and a hydrocarbon group such as an alkylene group an ester bond if the
Ku is an organic group (provided that binds to a silicon atom at the other end of the hydrocarbon group) bonded by a connecting bond of the preferred. Polyfluoroalkyl group, polyfluorooxaalkyl group,
And Porifuruorochi A alkyl group, the end bonded to a silicon atom or surrounding an alkylene group (particularly preferably a dimethylene group) der Li Kui other portions thereof based on perfluorinated, a is group.

The place for 1 Ataiyu machine group has a perfluoro moiety
If the moieties as the number of 3 or more perfluoroalkyl group having a carbon perfluoroalkyl oxaalkyl group, or preferably Pafuruorochi A alkyl group, particularly preferably a perfluoroalkyl group having 3 to 16 carbon atoms.

[0032] Specific examples of these Y and R ¹ to R ⁷ are, Ru include examples of the specific examples of the compound (A) below and the compound (B). Is the R _f in the following specific examples, in _{particular, C n F 2n + 1 C} m H 2m - ( provided that in this formula, n represents an integer of 3 to 16, m is an integer of 2 to 4.) In polyfluoroalkyl group is preferred having a perfluoroalkyl group moieties Table I <br/>, is a R _F in the following specific _{examples, C n F 2n + 1 -} ( where in the chemical formula, n 3-16 of integer.) is preferred.

Specific examples of the compound (A) and the compound (B) are shown below. However, compound (A) and compound (B) Lena had limited to these specific examples. In the following chemical formulas, x, n, and m are each an integer of 1 or more, R is an alkyl group, R _f is a polyfluoroalkyl group, and R is
_F is shows a perfluoroalkyl group, x is 2 to 8, R
Is preferably a lower alkyl group, and R _f is preferably a dimethylene group having a perfluoroalkyl group.

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]

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[0044]

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Illustrative of compound (B).

[0046]

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[0047]

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[0048]

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Further, in the present invention, in order to enhance the effect of the surface treatment with the isocyanate silane compound (I), it is preferable to use a treating agent containing an organopolysiloxane together with the isocyanate silane compound (I). As the organopolysiloxane, those called silicone oil or modified silicone oil are suitable. Hereinafter , this organopolysiloxane is also referred to as compound (D). Organopolysiloxane preferably has a polymerization unit which is I Table by the following formula (D).

[0050] ^{(D) [-Si (R 11} ) (CH 3) -O-] Note that, in this formula, R ¹¹ is to Table Wa organic group having 1 to 16 carbon atoms. The organic group same organic group as R ¹ to R ⁷ of the (however, those having no fluorine atom is preferred) is <br/> rather preferable, in particular, an alkyl group, an aryl group, an arylalkyl group, an amino Alkyl group, hydroxyalkyl group,
Or a hydrocarbon group having a polyoxyalkylene chain good <br/> better rather, especially lower alkyl groups are preferred.

The compound (D), having an isocyanate silane compound (I) treatment Ru improve the water droplet removal property and abrasion resistance of the coating film due to the effect of. This compound (D) preferably has no hydrolyzable group. Compound (D) may be used as it is as a treating agent , or may be added to the treating agent after being decomposed with an acid such as sulfuric acid, hydrochloric acid, or acetic acid. The viscosity of the organopolysiloxane compound (A), preferably be determined in consideration of the combination of the compound (B), a kinematic viscosity at particular 25 ° C. 0.
5 to 500 are preferred those centistokes (c S t).

[0052] While specific examples of the compound (D) below, Lena had limited to these.

[0053]

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[0054]

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[0055] In the present invention, the treatment agent of the first layer for forming for processing the surface of the second layer, the compound (A) or compound (B) of either compound required to things good
Good . Of course, even if both compounds are contained problem is not, percentage of that may be arbitrary. Also, any in accordance with the ratio of the compound in the case of added <br/> pressure to the compound (D) (D) and the compound (A) and / or <br/> others of compound (B) Purpose It is possible to Preferably, compounds (A), (B),
Total respect to the compound of (D) (D) or preferably the abundance of degradation products thereof and from 1 to 40 wt%. When the compound (D) is too small abrasion resistance, workability tends to decrease, and if too large, not only abrasion resistance is lowered, there is a risk that a feeling sticky when touched the surface remains.

[0056] Furthermore, compound (D), compound (A) Oyo
Beauty / or contributes to improving the durability of the enhancement and film of the water droplet removal property of the coating interaction with the teeth of compound (B). Although this detailed mechanism is unknown, the molecular chain of the compound (D) A compound (A) and compound (B) and complex entanglement, various organic groups present on the surface, in particular polar groups and ionic bonds It is considered that the result is to control the micro-distribution of, and to achieve an optimal surface structure for removing water droplets.

It is considered that the entanglement of molecules between the selected compounds greatly contributes to further increasing the durability. Compounds (A), (B) and (D)
Are both the front surface free energy lower material, it is also the wear resistance is good to reduce the frictional resistance of the surface by the compound in a free state which is present partially in the coating film moves very surface layer This is probably one of the causes.

[0058] The treating agent in the present invention, etc. Other compounds or additives are added depending on the purpose. The additive may be selected in consideration of the reactivity and compatibility with each component, and ultrafine particles of various metal oxides and various resins as described below can be added. If coloring is necessary, dyes, pigments, etc.
But it may also be added. These additives are compound (A),
0.01 to 100 parts by weight in total of (B) and (D)
20 parts by weight are preferable , and 0.1 to 5 parts by weight is particularly preferable . Excessive addition is undesirable because it reduces the water drop removal property, abrasion resistance and the like.

[0059] may be applied in the process of hand wiping or the like directly into the composition a second layer on the coating object, also, by the organic solvent, dissolving or be used to prepare a solution form of diluted Is also possible. In the solution using the organic solvent, the total amount of the compounds (A), (B), and (D) contained is determined in consideration of the film formability (workability), stability, film thickness, and economy. Is preferably 0.1 to 30% by weight.

As the organic solvent, various solvents such as acetates, aromatic hydrocarbons, halogenated hydrocarbons, ketones and ethers can be used, but they have a reactive functional group (such as a hydroxyl group). These compounds are not desirable because they react with the isocyanate groups contained in the compound (A) and the compound (B). However, an organic solvent having a functional group having low reactivity such as isopropyl alcohol can be used. The diluting solvent is not limited to one kind, and two or more kinds of mixed solvents can be used.

No special pretreatment is required for treating the surface of the second layer. The formation of the film is performed 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, etc. in air or nitrogen Motochu may be dried at room temperature. In particular, heating is preferably performed for the purpose of increasing the drying speed, increasing the durability, and the like. The heating temperature is preferably about 50 to 250 ° C, and the heating time is suitably 5 to 60 minutes. In the case of heating, the temperature and time may be set in consideration of the material of the second layer and the heat resistance of the base material.

[0062] In the present invention, an isocyanate silane compound (I) other than the hydrolyzable silane compound (II) or partial hydrolysis product thereof is used as a material for forming the second layer. The second layer below the first layer has the effects of improving the durability of the first layer and increasing the adhesion to the substrate. This second layer is usually formed on the substrate surface.

[0063] hydrolyzable silane compound (II) refers to a compound having a structure in which at least one hydrolyzable group bonded to a silicon atom. The compounds are those in which only the hydrolyzable groups to a silicon atom is bonded (eg example, tetraalkoxysilane) may be may be a compound that has at least one organic group to the silicon atom is bonded Good. However, the organic group in this case is preferably an organic group other than the organic group having a fluorine atom.

[0064] hydrolyzable silane compound (II) hydrolyzable in groups, Oh a group bonded to the silicon atom Rika
This is a group that reacts with water and is eliminated to form a hydroxyl group (silanol group) bonded to a silicon atom. Examples of the hydrolyzable group include, for example, a halogen atom, an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group, an aminoxy group ,
Examples include an acid amide group and a ketoxime group. Preferably, an alkoxy group, an alkoxy-substituted alkoxy group, reed <br/> Le hydrolyzable group bonded to a silicon atom by an oxygen atom, such as a group. The number of carbon atoms of these hydrolyzable groups is preferably 8 or less, particularly 4 or less. Preferred hydrolyzable groups are alkoxy groups having 4 or less carbon atoms (hereinafter also referred to as lower alkoxy groups).

[0065] The partial hydrolysis product of the hydrolyzable silane compound (II), the hydrolyzable sila with water or an acidic aqueous solution
Compounds having a silanol group that raw <br/> formed by emission compound (II) is partially hydrolyzed, or refers to a compound in which two or more molecules condensed by the reaction of the silanol groups. Examples of the acid include hydrochloric acid, acetic acid, phosphoric acid, nitric acid,
Sulfuric acid, wear, etc. is for the use sulfonic acid.

Hereinafter, the hydrolyzable silane compound (II), which is an essential component for forming the second layer, will be referred to as compound (C).
Also called. The compound (C) compounds I Table by the following formula (C) are preferred.

(C) (R ⁸ ) _i (R ⁹ ) _j (R ¹⁰ ) _k SiX _{4-ijk wherein} X is a hydrolyzable group, and R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or organic group, i, j, and k are independently 0, 1, 2 or 3 der Li Kui 0 ≦ i + j + k,
Represented by an integer satisfying ≦ 3.

[0068] When R ⁸ to R ¹⁰ is an organic group is preferably the same organic groups as the R ¹ to R ^7. As the organic group, a hydrocarbon group is suitable, a hydrocarbon group having 1 to 6 carbon atoms is preferable, and an alkyl group is most preferable. The organic group is preferably a radical having no fluorine atom, but a fluorine
It is a group having an atomic not good. Further, the organic group may be an organic group having a functional group such as an amino group or an epoxy group. Further, i + j + k is preferably 0 to 1. Particularly preferred compound (C) Ri compound der of i + j + k = 0,
Most preferably, it is a tetraalkoxysilane.

The silanation having only these hydrolyzable groups
Compound,OrIts partial hydrolysis productsTouseif you did this
Is,It is excellent in compatibility and adhesion with the first layer.Mochi
RonUse of this compound in combination with other silane compounds,LaterDo
A favorable second layer is also formed by the addition of the additional component.

[0070] While specific examples of the compound (C) below, the compound (C) is Lena have limited thereto.

[0071] tetramethoxysilane, tetraethoxysilane, tetra (n- propoxy) silane, tetra iso-flop <br/> Ropoki shish run, tetra (n- butoxy) silane, tetra (sec-butoxy) silane, tetra (t- Tetraalkoxysilanes such as butoxy) silane.

[0072] methyltrimethoxysilane, methyltriethoxysilane, et triethoxysilane, vinyl trimethoxysilane, phenyl triethoxysilane, .gamma.-chloropropyl trimethoxy silane, .gamma.-chloropropyltriethoxysilane, 3,3,3 - trifluoropropyl trimethoxy silane, chloromethyl trimethoxy silane, chloromethyl triethoxy silane, gamma - methacryl b
Lee Le trimethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, .gamma.-mercaptopropyl triethoxysilane, .gamma.-aminopropyltrimethoxysilane, .gamma.-aminopropyltriethoxysilane, N
- (beta - A Minoechiru)-.gamma.-aminopropyltrimethoxysilane, beta-cyanoethyl triethoxy silane,

Glycidoxymethyltrimethoxysilane ,
Grayed Licid carboxymethyl methyltriethoxysilane, alpha-glycidoxyethyl trimethoxysilane, alpha-glycidoxypropyl triethoxysilane, beta-glycidoxyethyl trimethoxysilane, beta-glycidoxyethyl triethoxysilane, alpha- Glycidoxypropyltrimethoxysilane,
α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane,

Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropyltripropoxysilane, γ-
Glycidoxypropyl tributoxysilane silane, alpha - Gurishidoki Shiv trimethoxysilane, alpha-glycidoxybutyl triethoxysilane, beta-glycidoxy butyl trimethoxy silane, beta-glycidoxy butyl triethoxysilane, .gamma. Gris Sidoxybutyltrimethoxysilane,
γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane,

(3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyl tripropoxysilane, β- (3,4-epoxycyclohexyl)
Ethyltributoxysilane , γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ-
(3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl)
Trialkoxysilanes such as butyltrimethoxysilane and δ- (3,4-epoxycyclohexyl) butyltriethoxysilane;

[0076] methyltriacetoxysilane, vinyltriacetoxysilane, phenyl triacetoxy silane, gamma
- tri scan such chloropropyl triacetoxysilane
( Acyloxy ) silanes.

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

[0078] dimethyldimethoxysilane, phenylmethyl dimethoxysilane, dimethyl diethoxy silane, phenyl methyl diethoxy silane, .gamma.-chloropropyl methyl dimethoxy silane, .gamma.-chloropropyl methyl diethoxy silane, .gamma. main Taku Li acryloyloxy propyl methyl dimethoxysilane, .gamma. methacryl acryloyloxy propyl methyl diethoxy silane,

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

Glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldimethoxysilane, α-
Glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane,

Γ-glycidoxypropylmethyldimethoxysilane , γ -glycidoxypropylmethyldiethoxysilane , γ -glycidoxypropylmethyldipropoxysilane , γ -glycidoxypropylmethyldibutoxysilane , γ -glycid Xypropylethyldiethoxysilane, γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, etc. dialkoxy silanes.

Bis such as dimethyldiacetoxysilane and γ-glycidoxypropylmethyldiphenoxysilane
( Acyloxy ) silanes and diphenoxysilanes.

The hydrolyzable silane compound (I)
The surface treated with I) or a partial hydrolysis product thereof, those of compounds is chemically, or refers to a physically bound surfaces. Since hydrolyzable groups ing a silanol group is decomposed by water, these compounds are believed to primarily binds to the surface by chemical reaction of the silanol groups. For example, the silanol group is considered to dehydration condensation reaction with the silanol groups on the glass surface. It is also considered that the first layer also bonds to silanol groups on the surface of the second layer.

[0084] As the treating agent for forming the second layer is a treatment agent containing a hydrolyzable silane compound (II) or a partial hydrolysis product, the form of a solution or dispersion
Preferred treatment agents are preferred. The treatment agent containing a solvent or dispersing agent, Ru <br/> can other additives to be al in addition a solvent or dispersant added pressure. As the solvent, a solvent having a functional group capable of reacting with an isocyanate group may be used in addition to the above-described solvents. As the additive, specifically, for example, fillers fine particles of the metal oxide, a binder component, and a surfactant. The above-mentioned ratios are also appropriate for their use ratio. Further, it is preferable that the used amount is the same as the above. The treating agent for forming the second layer is preferably a composition that does not substantially contain the isocyanate silane compound (I).

[0085] As additive pressurizing agent, silica, aluminum oxide, fine particles of metal oxides such as zirconium oxide is preferably
Ku, in particular ultrafine particles are preferred in the sol, such as silica sol or Ariminazoru, as other filler component, epoxy resins, unsaturated polyester resins, polyurethane resins,
It is preferable to use a binder component such as (meth) acrylates.

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

The second layer is formed by applying the prepared treating agent to the surface by an ordinary treatment method, for example, by various methods such as brushing, flow coating, spin coating, dip coating, spray coating and the like. or nitrogen Motochu, or preferably dried by heating at room temperature. Furthermore when performing firing under a dry temperature or preferably further heated to a high temperature. When heating, it is preferable to set the temperature and time in consideration of the heat resistance of the substrate.

[0088] coating or silane compound volatilization subsequent solvent contacts the substrate surface hydrolysis of the substrate surface - considered reaction binding occurs. In this case, drying after application may be at room temperature, may be dried by heating, and
The formed layer may be fired. Heat drying or calcination temperature is preferably 200 ° C. or less, the time is preferably less 120 hours. Hot heating Ri linseed, or there is a negative effect on the adhesion of the long <br/> when subjected to heat first and second layers.

[0089] The thickness is particularly LIMITED Lena bur of the second layer generated by this surface treatment, or may be very thin. Preferred layer thickness is less than 2 0μ m, less 2.mu. m is particularly preferred. The lower limit is the monolayer thickness.
However, the second layer may be thicker. The layer thickness can be adjusted to a desired thickness by adjusting the concentration of the layer forming component in the treatment agent , application conditions, heating conditions, and the like.

[0090] The thickness of each layer formed dark time the treatment agent, coating conditions may be suitably controlled depending on the heating conditions. The present invention
The first layer is relatively refractive index is low in, hence low reflectivity are also imparted. When to expect such effects have good by controlling the film thickness of the film thickness of the first layer optical interference occurs. In particular, the film thickness of the film in theory to express the water droplet removal property is sufficient if more monomolecular layers, which in economic effect is desirable the or less 2.mu. m as in consideration.

[0091] The substrate having such a layer as or an article for transportation equipment can be easily mounted as a part thereof.
For example, train body, window glass, pantograph, etc.
It can be easily used as a body of a car (truck), a windshield, a rear glass, a side glass, a mirror, a bumper, a ship body, a window glass, an aircraft body, a window glass, and the like.

[0092] In the front surface treated substrate, repelled water drops attached to the surface by water droplet removal property, in particular, rapidly move on the surface by interaction with the wind pressure with the operation, collect as water droplets Without this, it is possible to eliminate the adverse effects induced by moisture. In particular, when the base material is used for a transparent field of view such as a window glass , the scattering of water droplets makes it very easy to secure a visual field, which can lead to an improvement in vehicle safety . Further, even in an environment where water droplets freeze, thawing does not occur. In addition, it is possible to reduce the periodic cleaning operations count for adhesion there is little water droplet, moreover, cleaning is very advantageous from a very easy, aesthetic retention points.

[0093]

EXAMPLES Hereinafter, specific description is but the present invention is Lena have limited only to embodiments of the present invention through examples. Example
It was carried out in kicking various evaluation Hatsu technique of way.

1. Water Drop Removability (1 ) The falling angle of a water droplet 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 tester: Taber type rotary abraser (Toyo Seiki Seisakusho Co., Ltd.). Test conditions: Wear wheel H-22, load 1 kg, wear frequency 30
0 times. It was evaluated repellency after performing the abrasion test by the method described above.

3. Weathering test UV irradiation was performed for 8 hours (70 ° C) and wet exposure was performed for 4 hours (5 hours).
The 0 ° C.) to process as one cycle, 200 cycles
It was to evaluate the water droplet removal property after the actual applied.

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

5. Compound to be used (a) Si (OCH ₃ ) ₄ (b) Methanol-dispersed silica sol (solid content: 30% by weight, manufactured by Catalyst Chemicals, Inc.) (c) C ₈ H ₁₇ Si (NCO) ₃ (d) C ₈ F ₁₇ CH ₂ CH ₂ Si (NCO) ₃ (e) (OCN) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (NCO) ₃ (f) Si (NCO) ₄ (g) (CH ₃ ) ₃ SiO -[Si (CH ₃ ) ₂ -O-] _n -Si (CH ₃ ) ₃ [Kinematic viscosity 50
cSt]

[Preparation of treating agent 1] In a three-necked flask in which a stirrer and a thermometer were set,
(a) 78.5 g, 1020.2 g of methyl alcohol and 2000.0 g of isopropyl alcohol were added and stirred for 1 hour. While maintaining the temperature of the solution at 5 ° C., 37.2 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After completion of the dropwise addition, stirring was continued for 5 days while maintaining the liquid temperature at 25 ° C. to obtain a treating agent 1.

[0102] The 3-necked flask Preparation of treatment agent 2] stirrer and a thermometer,
(a) 75.0 g, (b) 10.9 g, methyl alcohol 1203.5 g,
2000.0 g of isopropyl alcohol was added and stirred for 1 hour. While maintaining the temperature of the solution at 5 ° C., 35.5 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After dropping, the liquid temperature is set to 25 ° C
The stirring was continued for 5 days while maintaining the temperature to obtain a treating agent 2.

[0102] In the treating agent Preparation of 3] stirrer and thermometer is set flask, (c) 2
Added 0.0g and butyl acetate 1980.0G, the liquid temperature of this solution 2
While maintaining the temperature at 5 ° C., stirring was continued for one day to obtain a treating agent 3.

[0103] In the preparation of the treatment agent 4] stirrer and thermometer is set flask, (d) 1
A mixture of 9.9 g and 10.3 g of (e) was added, and ethyl acetate was further added.
985.3 g, 54.2 g of isopropyl alcohol, and 456.3 g of trichlorotrifluoroethane (R-113) were added, and stirring was continued for 5 days while maintaining the solution temperature at 25 ° C. to obtain a treating agent 4.

[0104] In the treating agent Preparation of 5 stirrer and thermometer is set flask, (c) 9.8
g, (f) 2.4 g, and (d) 9.8 g were mixed and added. Further, butyl acetate 970.0 g, isopropyl alcohol 35.5 g,
200.0 g of trichlorotrifluoroethane (R-113)
Was added, and the solution was stirred for 24 hours while maintaining the solution temperature at 25 ° C. to obtain a treating agent 5.

[0105] In the preparation of the treatment agent 6] stirrer and thermometer is set flask, (d) 1
A mixture of 9.9 g and 10.3 g of (e) was added, and ethyl acetate was further added.
985.3 g, 54.2 g of isopropyl alcohol and 456.3 g of trichlorotrifluoroethane (R-113) were added, and then 1.8 g of (g) and 0.2 g of sulfuric acid were further added, and the solution temperature was maintained at 25 ° C. Stirring was continued for 5 days to obtain a treating agent 6.

Example 1 A glass plate of 10 cm × 10 cm (thickness: 3 mm) was immersed in a solution of the treating agent 1, pulled up at a rate of 11 cm / min , and heated at 80 ° C. for 10 minutes. After leaving this test piece at room temperature for 30 minutes, it was immersed in a solution of the treating agent 3, pulled up at a speed of 11 cm / min , and heated at 150 ° 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 3 in Example 1 was changed to the treating agent 4. The results are shown in Table 1.

Example 3 A test and evaluation were performed in the same manner as in Example 1 except that the treating agent 3 in Example 1 was changed to the treating agent 5. The results are shown in Table 1.

Example 4 A test and evaluation were conducted in the same manner as in Example 1 except that the treating agent 3 in Example 1 was changed to the treating agent 6. The results are shown in Table 1.

Example 5 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 shown in Table 1.

Example 6 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 and the treating agent 3 was changed to the treating agent 4. The results are shown in Table 1.

Example 7 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 and the treating agent 3 was changed to the treating agent 5. The results are shown in Table 1.

Example 8 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 and the treating agent 3 was changed to the treating agent 6. The results are shown in Table 1.

Example 9 A test and evaluation were performed in the same manner as in Example 1 except that the heating after dipping of the treating agent 1 in Example 1 was changed from 80 ° C. for 10 minutes to 300 ° C. for 30 minutes. The results are shown in Table 1.

Comparative Example 1 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 11 cm / min to prepare a sample test piece. Table 1 shows the results of evaluating the test pieces.

[0116]

[Table 1]

Example 10 The test piece obtained in Example 3 was immersed in the chemicals shown in Table 2 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 2 shows the results.

[0118]

[Table 2]

Example 11 A coating was formed on the surface of a front laminated glass for an automobile by the method of Example 3 . The obtained front laminated glass was mounted on the front of a car. Using this car , a four-hour daytime running test was performed for one month, and the state of dirt and dust on the front surface and the state of water droplets on rainy days were visually observed every day .

[0120] As a result, dirt, dust adhesion of, the occurrence of water plaque by the attachment of the water droplets was not observed at all, were rarely easily removed by wiping gently with even tee Tsu tissue paper in their occurrence was observed . Further, at the time of rainy weather moved quickly by an interaction with wind pressure by water droplets are repelled running surface, viewing without using a wiper is secured.
Water droplets adhering to freezing the laminated windshield untreated Additionally, or front in the running test in an environment such that icing on the windshield moisture in the air is condensed (0 ℃ ~-5 ℃) No icing on the glass was observed.

[0121] Under severe low-temperature environment to further (-10 ℃ ~-1
(5 ° C.), icing on the windshield was also observed, but the thawing was fast and there was a marked difference compared to the untreated windshield.

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

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

[0124]

The base material for transport equipment and the article for transport equipment of the present invention and the transport equipment equipped with them are described in Examples .
As can be seen, an excellent effect is observed. That is, 1. It has excellent water droplet removal property, dust, dirt, water droplets adhesion of, or no such it by water stain generation, rarely even their occurrence, blocking the adverse effects of easily removable inducible water Cleaning can be simplified. 2. It has excellent durability of removing water droplets and maintains its state semipermanently.

[0125] 3. Excellent chemical resistance, use of in along the coastline, or even be effective in a ship touching seawater directly. 4. No special pretreatment is required, and the economic effect is high. Above effects are those which can not be expected with conventional materials, cut with expanding its application range to the field was not previously used.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08J ^7/ 04-7/06

Claims (11)

(57) [Claims] [Claim 1] consists of treated substrate having at least two treated surface layers on the substrate surface, or as a component of the treated substrate, an article for transportation equipment, the outermost layer of the surface treatment layer The first layer contains the isocyanate silane compound (I) .
A layer obtained by treating untreated agent, the second layer is a hydrolyzable silane compound is a lower layer in contact with the outermost layer (II) or
The other is a layer obtained by treating with a treating agent comprising a partial hydrolysis product, transportation equipment article. Wherein the substrate transport device for article according to 請 Motomeko 1 Ru glass der. 3. The method according to claim 1, wherein the isocyanate silane compound (I) is,under
Notation (A)Compound represented byOrThe following formulaTable in (B)
ICompoundRuClaim 1Or described in 2Transport
Equipment goods. (A) (OCN)_3-ab(R¹)_a(R^Two)_bSi-Y-Si (R^Three)_c(R^Four)_d(NCO)_3-cd  Where R¹ , R^Two , R^Three ,andR^Four Independently,hydrogen
atomOr 1 carbon~16 organic groups, aandb is independent
To,0, 1,Or2RikatsuSatisfies 0 ≦ a + b ≦ 2
Integer, candd is independent,0, 1,Or2R
AndInteger satisfying 0 ≦ c + d ≦ 2, YIs 2WorthShow machine base
I forgot. (B)(R ^Five ) _e (R ⁶ ) _g (R ⁷ ) _h Si (NCO) _4-egh  Where R^Five , R⁶ ,andR⁷ Independently,hydrogenatomMa
Or 1 carbon~16 organic groups, e, g,andh is independent
To,0, 1, 2,Or3Rikatsu0 ≦ e + g + h ≦
Represents an integer satisfying 3. (4)Isocyanate silane compound (I)formula
(A)Kick2 wherein Y has two or more fluorine atomsWorth
MachineCompound,R in formula (A) ¹ , R ^Two , R
^Three , And R ^Four At least one of which is a polyfluoroalkyl
Organic groupCompound,OrEquation (B)
R ^Five , R ⁶ , And R ⁷ At least one ofButPolyph
It is an organic group having a fluoroalkyl groupCompound,Is
ClaimDescribed in 3Goods for transportation equipment. 5. The method according to claim 1, wherein the first layer is a treating agent containing an organopolysiloxane together with the isocyanate silane compound (I).
5. A layer obtained by processing.
Transportation equipment for the article according to. 6. An organopolysiloxane represented by the following formula (D):
A repeating structural unit represented in, and transport equipment article according to 請 Motomeko 5 kinematic viscosity Ru organopolysiloxane der of 0.5 to 500 centistokes at 25 ° C.. (D) [—Si (R ¹¹ ) (CH ₃ ) —O—] wherein R ¹¹ represents an organic group having 1 to 16 carbon atoms. 7. The hydrolyzable silane compound (II) is, Ru compound der represented by the following formula (C) 請 Motomeko 1-6 noise
An article for transport equipment according to any of the preceding claims. (C) (R ⁸ ) _i (R ⁹ ) _j (R ¹⁰ ) _k SiX _{4-ijk wherein} X is a hydrolyzable group, and R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or an organic group; i, j, and k are independently 0, 1, 2 or 3 der Li Kui 0 ≦ i + j + k,
Represents an integer satisfying ≦ 3. 8. The transportation device according to claim 7, wherein X is a hydrolyzable group selected from a halogen atom, an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group, an aminoxy group , an acid amide group, and a ketoxmate group. For goods. 9. The thickness of the first layer is from a monolayer thickness to 2 μm.
An article for transportation equipment according to any one of claims 1 to 8. 10. The layer thickness of the second layer is from a monolayer thickness to 2 μm.
An article for transportation equipment according to any one of claims 1 to 9. 11. A hydrolyzable silane compound (II) or a partial hydrolysis product thereof on a surface of a substrate for an article for transportation equipment .
The second layer was formed by treatment with a treating agent containing, then the front surface processing layer a second layer surface to form a first layer is treated with a treating agent <br/> containing an isocyanate silane compound (I) A method for manufacturing an article for transportation equipment.