JP3155025B2 - Surface-treated building / building article and method of manufacturing the article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a small adhesion of water droplets,
Or long-term easy repellent surface removal of water drops attached
Architecture and Ken wearing article can be maintained I cotton, and the architectural and
About the manufacturing method of construction wearing article.

[0002]

BACKGROUND OF THE INVENTION house, building, there is a component of the other of the exterior member and the interior member of a building, construction Tsukibutsu of interior and exterior, furniture, building and construction wearing articles of furniture, and the like, or architecture and construction wearing article, it is preferred substrate, the surface of the is always clean. Raindrops,
Dust, or dirt adhesion, the moisture is condensed by the influence of temperature and humidity in the atmosphere, the appearance is impaired Q
There is a title . If the architectural / building article has 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 building and construction wearing article surface, building and construction wearing article transparency, articles that require fluoroscopic wild (e.g., window glass or mirrors, etc.) If it is, the lead that the original purpose object product can not be achieved.

[0004] means for removing water drops, etc. (e.g., removal by wiping) may be given a fine scratches on the front side. Further, the foreign particles are accompanied by water drops, damage
There is also Kunar problem wrote. 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 original function, also, inconvenience in terms of the scattering is intense field secure light on its surface.

[0005] and other moisture can damage adversely affect the surface of the building and construction wearing article, contamination, colored, to promote corrosion and electrical characteristics of the building and construction wearing article, mechanical properties In some cases, a change in optical characteristics or the like may be induced.

In order to solve such a problem , the construction
Imparting properties are also low Kusuru property of adhesion of water droplets to the construction wearing article surface to facilitate the removal of water droplets attached (hereinafter referred to simply water droplet removal property) is that strongly demanded. So
To make the surface more water-removable than before
Te, for example, silicone over down oil consisting of silicone over emissions wax or an organopolysiloxane, or a surfactant 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 building and construction wearing article is fabricated future, measures need a lecture Jill even for already building and construction wearing article being used . The building and construction wearing article is already in use, it is necessary to apply a water drop removal property simply by directly treated with normal <br/> temperature. For example, window glass already attached to a building
To swap the line cormorant If, window glass processing in is economically disadvantageous, also, it is practically impossible to firing the part after application. From this point of view Ru difficult der correspond with conventional surface <br/> 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,
In addition, it has been confirmed that various substrates treated with the treating agent are extremely suitable as substrates having a water-drop removing property, particularly as building and building articles, and have completed the present invention . The present invention has a property of removing water droplets, and is excellent in abrasion resistance, chemical resistance, and weather resistance, and its effects are semipermanently maintained , and a method for manufacturing the article . The purpose is to provide.

[0010]

Means for Solving the Problems The present invention is the following invention which has achieved the above object.

[0011] Namely, the present invention consists of treated substrate having at least two treated surface layers on the substrate surface, or the
A building / building article having a treated substrate as a component, wherein the first layer, which is the outermost layer of the surface treatment layer, has an organic group having two or more fluorine atoms and a hydrolyzable group. silane compound (I) or a layer obtained by treating with a treating agent comprising a partial hydrolysis product, the second layer is a fluorine-containing organosilane of a lower layer in contact with the outermost layer
Compound (I) other than or tetraalkoxysilane is a layer obtained by treating with a treating agent comprising a partial hydrolysis product, building and construction wearing article, and the article manufacturing method Hisage
Offer .

[0012] Contact Keru fluorinated organosilane compound according to the present invention and (I) is an organic group having at least one more fluorine atoms, and at least one hydrolyzable group is the same or bonded to different silicon atoms Refers to a compound having the following structure. Organic groups and silicon atoms are replaced by carbon atoms and silicon
The bond is formed by bonding with an atom, and the hydrolyzable group is also directly bonded to the silicon atom. Organic groups and silicon atoms may be bonded to different silicon atoms within the same molecule (in this case, having two or more silicon atoms in the same molecule), may be bonded to the same silicon atom.

An organic group other than an organic group having two or more fluorine atoms may be bonded to the silicon atom. 2
An organic group having more fluorine atoms is normally a monovalent organic group, a divalent or coupling between two silicon atoms may be higher-valent organic group.

The hydrolyzable silane compound (II) refers to a compound having a structure in which at least one hydrolyzable group is 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 an organic group other than the organic group having two or more fluorine atoms.

The fluorine-containing organosilane compound (I) and
The hydrolyzable group in the hydrolyzable silane compound (II) is a group bonded to a silicon atom, and is a group that reacts with water and is eliminated to generate a hydroxyl group (silanol group) bonded to the silicon atom. . The hydrolyzable group, for example, a halogen atom, an alkoxy group, an acyloxy group, an alkoxy-substituted alkoxy group, an aminoxy group, an acid amide group or Ru ketoximate group and the like. Preferably, an alkoxy group, substituted alkoxy group, a hydrolyzable group bonded to a silicon atom by an oxygen atom, such as an acyl group <br/>. The number of carbon atoms of these hydrolyzable groups rather preferably 8 or less,
Particularly, 4 or less is preferable . Preferred hydrolyzable groups, the number 4 an alkoxy group having a carbon (hereinafter, referred to as a lower alkoxy group).

The fluorine-containing organosilane compound (I) or
Is a hydrolyzable silane compound (II) (hereinafter referred to as
This is called a silane compound having a hydrolyzable group. ) And partial hydrolysis products, hydrolysis with water or an acidic aqueous solution
Compounds having a silanol group to produce a silane compound having a sex groups partially hydrolyzed, or refers to a compound molecules to two or more are condensed by the reaction of the silanol groups. Examples of the acid include hydrochloric acid, acetic acid, phosphoric acid, nitric acid,
Sulfuric acid, and sulfonic acid wear in use.

[0017] The surface treated with a silane compound having a pressurized water-decomposable group or its partial hydrolysis product, the compound chemically, or refers to a physically bound surfaces. Since hydrolyzable groups ing a silanol group is decomposed by water,
The compound is believed to primarily binds to the surface by chemical reaction of the silanol groups. That is , this silanol group is considered to undergo a dehydration condensation reaction with the silanol group on the glass surface. It is also considered that the first layer also bonds to silanol groups on the surface of the second layer .

[0018] with our Keru building and construction wearing article of the present invention, the article to be attached to construction <br/> built product, article that is already installed in the building, Moshiku is without attached directly to the building A building article used together with a building, a building article such as furniture or furniture, or a base material (such as a glass plate) that is a component of the article. Specifically, it is used in place of window glass and window glass, roof glass and glass roof, door glass and doors in which it is installed, partition glass, greenhouse glass and greenhouse, and glass Transparent plastic plate and the above-mentioned architectural articles (window materials and roofing materials) having the same, wall materials made of ceramics, cement, metal and other materials, mirrors and furniture having the same, or display shelves and shows like glass or the like for the case
Is Ru.

[0019] Building, construction wearing article may be composed solely of processing <br/> substrate surface-treated, or may be surface-treated treated substrate is incorporated. For example, the former is a window glass plate, and the latter is furniture incorporating a glass mirror.

The type of substrate of the building and construction wearing article particularly limited <br/> is Lena are. For example, metal, plastic, glass, inorganic materials and organic materials such as ceramics, also Waso these combinations (composites, layered materials, etc.). Surface also substrate may be a surface of the substrate itself, different from the front surface of the <br/> substrate itself such as the surface of the surface treated layer of the coating film surface and surface-treated glass, such as painted metal plate The surface may be made of a material. Also, any shape as the shape of the substrate corresponding to the flat plate, the total surface or partially purposes, such as those having a curvature
Is mentioned .

[0021] 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 building and construction wearing article according to the present invention is preferably an article utilizing the transparency of the transparent material, for example, include a window member made of glass or transparent plastic or the like, roof materials, mirrors, and the like
Is Ru. These raindrops, dust, due to the adhesion of dirt, perspective wild is rather ease reduced risk there Ru to its Reniyo Ri problems. Glass is particularly preferred as the substrate.

The surface treatment is usually performed on a surface having a hydrolyzable group.
Orchid compound or containing a partial hydrolysis product of the compound
The processing agent is applied to the surface, preferably carried out by coupling these of compounds on the surface. The treating agent is preferably a solution containing a solvent. Other components can be present in the solution. Examples of other components, for example, Ru include bar Indah component or metal oxide particles will be described later.

The coating also the treatment agent to the substrate surface are shorted with a volatilization subsequent solvent, of compound contacts the substrate surface, believed to hydrolysis and formation Gohan response occurs. In this case, drying after application may be performed at room temperature, may be performed by heating and drying, or the formed layer may be baked. Heat drying or calcination temperature is preferably 200 ° C. or less, the time is preferably less 120 hours. High temperature of heating to Ri sweet,
Or when subjected to heat a long time, (especially the second layer, adhesion to the second layer of the first layer) adhesion layers are negatively affected.

The thickness is particularly LIMITED Lena bur of the surface treatment layer generated by this surface treatment, at least the first layer is preferably extremely to thin it. The preferred thickness of the first layer is
20 [mu] m or less, particularly less 2.mu. m. The lower limit is the monolayer thickness. Of course, a binder component and metal oxide fine particles often compounded, can be thicker layer thickness. Preferably, the second layer also has the same thin layer thickness as the first layer. However, the second layer can be thicker. The layer thickness is determined by the concentration of a layer forming component in a processing agent such as a solution,
The thickness can be adjusted to a desired thickness by application conditions, heating conditions, and the like.

Preferred compounds as the fluorine-containing organosilane compound (I) are compounds having one or two silicon atoms to which a hydrolyzable group is bonded. Preferred fluorinated organosilane 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) X_3-ab(R¹)_a(R^Two)_bSi-Y-Si (R^Three)_c(R^Four)_dX_3-cd Wherein X is a hydrolyzable group, R¹ , R^Two , R^Three ,and
R^Four Independently,hydrogenatomOr 1 carbon~16 organic
Group, aandb is independently,0, 1,Or2Rikatsu
An integer satisfying 0 ≦ a + b ≦ 2, candd is independent,
0, 1,Or2RikatsuInteger satisfying 0 ≦ c + d ≦ 2
number, YIs 2WorthRepresents a machine, Y orIs R ¹~ R^Four Little
At least oneIsAn organic group having two or more fluorine atoms
is there.

(B)(R _f ) _e (R ^Five ) _g (R ⁶ ) _h SiX _4-egh  Wherein X is a hydrolyzable group, R_f Is two or more fluorine atoms
An organic group having^Five andR⁶ Independently,hydrogenatomMa
Or 1 carbon~16 organic groups, e is 1, 2,Or3,
gandh is independent,0, 1, 2,Or3Rikatsu
Represents an integer satisfying 1 ≦ e + g + h ≦ 3.

Compound (A) is a compound having two silicon atoms bonded to a hydrolyzable group, and compound (B) is a compound having one silicon atom bonded to a hydrolyzable group. Preferably, R ¹ to R ⁶ is an organic group. All R ¹ to R ⁶ in particular is present is preferably an organic group.

When two or more hydrolyzable groups X are present in the molecule , each hydrolyzable group may be different. Rice cake
N, compound (A), compound (B), and the hydrolyzable group X in the later-described compounds <br/> compound (C) also may be different from each other. In the compound (A) and the compound (B),
Hydrolyzable silicon-bonded groups or two or Ah silicon atom. Binding to the substrate surface as the hydrolyzable groups often it is thought to become a firm.

[0030] R _f is a 1 Ataiyu <br/> machine group having 2 or more fluorine atoms, as the base polyfluoroalkyl group, polyfluorooxaalkyl group, Porifuruorochi A alkyl <br/> group, or either of these groups and hydrocarbon groups and organic groups bonded by a connecting bond which ester bonds or discussed later such as an alkylene group (provided that binds to a silicon atom at the other end of the hydrocarbon group). Polyfluoroalkyl group, polyfluorooxaalkyl group, and Porifuruorochi A alkyl group, the end bonded to a silicon atom or surrounding an alkylene group (in particular, preferably dimethylene group
No. ) 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. When e is 2 to 3, a plurality of R _f may be different.

[0032] R ¹ to R ⁴ is an organic group is preferable, discussed later to Y is 2 Ataiyu machine group other than group having 2 or more fluorine atoms
In some cases, one even without least of R ¹ to R ⁴ must be 1 Ataiyu machine group having 2 or more fluorine atoms. 1 Ataiyu Kimoto having two or more fluorine atoms is equivalent organic group and R _f (hereinafter to Table Wa 1 Ataiyu machine group R _f having two or more fluorine atoms in the compound (A) ) Is preferred .

[0033] R ¹ to R ⁴ is an organic group other than R _f spot <br/> case, examples of the organic group, an alkyl group, an alkenyl group, a cycloalkyl group or a hydrocarbon group such as an aryl group, chloro A halogenated hydrocarbon group other than R _f such as an alkyl group,
A hydroxyl group, an epoxy group, an amino group, a mercapto group, or a (halogenated) hydrocarbon group having a functional group such as a carboxyl group, or an ester bond, an ether bond, a thioether bond, an imino bond in the middle of a carbon chain, (Halogenated) hydrocarbon groups having a linkage such as an amide bond are preferred.

Further, the organic group is preferably a hydrocarbon group or a hydrocarbon group having a functional group. Preferred hydrocarbon groups include alkyl group having 1 to 16 carbon atoms, and aryl groups rather preferable, in particular, alkyl group having 4 or less carbon atoms (hereinafter, referred to as lower alkyl groups) rather preferred, especially methylcarbamoyl <br Phenyl groups are preferred .

R ^{5 to} R ⁶ are an organic group having 1 to 16 carbon atoms.
If that is preferably an organic group other than R _f, groups of the same <br/> such an organic group other than R _f in R ¹ to R ⁴ above is preferably a said organic group.

[0036] Y when it is 2 Ataiyu machine group having 2 or more fluorine atoms, examples of the divalent organic group polyfluoroalkylene group, polyfluoro oxaalkylene group (the carbon chain of the alkylene group intermediate to at least one group ether bond is present), or Porifuruorochi a alkylene group (at least one group thioether bond is present in the middle of the carbon chain of the alkylene group) is preferable.

In particular, divalent organic compounds having two or more fluorine atoms
The group moiety bonded to the silicon atoms at both ends is a polymethylene group (particularly dimethylene group), their middle portion perfluoroalkylene group, perfluoro oxaalkylene group, or divalent is Pafuruorochi A alkylene group organic group is preferred. These Y have 6 to 3 carbon atoms.
0 is preferable , and especially 6 to 16 is preferable. Also, if Y is 2
More field <br/> If a group other than 2 Ataiyu machine group having a fluorine atom, as the base, an alkylene group, an oxaalkylene group or Chi A alkylene group, is preferable. The carbon number is preferably from 2 to 30, particularly preferably from 2 to 16.

Specific examples of R _f , R ^{1 to} R ⁶ and Y are as follows :
Examples in the following specific examples of compounds (A) and (B) is Ru mentioned. Is the R _f in the following specific examples, in particular, C
_n F _{2n + 1} C _m H _2m- (However, in this chemical formula, n
Is an integer of 3 to 16, and m is an integer of 2 to 4 . Polyfluoroalkyl group is preferred having a perfluoroalkyl group moieties I Table in), is a R _F in the following specific examples, in _{particular, 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 formula, x, n, and m are each an integer of 1 or more, X is a hydrolyzable group, R is an alkyl group, R _f is a polyfluoroalkyl group, and R _F is a perfluoroalkyl group. Show. In these chemical formulas, x is preferably 2 to 8, X is a lower alkoxy group, R is a lower alkyl group, and R _f is a dimethylene group having a perfluoroalkyl group.

Illustrative of compound (A).

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

Embedded image Illustrative of compound (B).

[0050]

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[0051]

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[0052] Further, in the present invention, the fluorine-containing organosilane compounds as a material for forming the second layer
(I) other than the hydrolyzable silane compound (II), one of the
Or tetraalkoxysilane is the that use a partial hydrolysis product. 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. Hereinafter , the hydrolyzable silane compound (II) is also referred to as compound (C) . Of compound (C) is compounds I Table by the following formula (C) are preferred.

(C)(R ⁷ ) _i (R ⁸ ) _j (R ⁹ ) _k SiX _4-ijk  Wherein X is a hydrolyzable group, R⁷ , R⁸ ,andR⁹ Is
Independently,hydrogenatomOr 1 carbon~16 organic groups (just
And is not an organic group having two or more fluorine atoms),
i, j,andk is independent,0, 1, 2,Or3
RikatsuRepresents an integer satisfying 0 ≦ i + j + k ≦ 3.

[0054] R ⁷ ~R ⁹ nitrous an organic group having 1 to 16 carbon atoms
If that is preferably Ru organic radical der not R _f,
The same as the organic groups other than the R _f group in the above R ^{1 to} R ⁴
Groups are preferred. Particularly preferred compound (C) is i + j + k
= Ri compound der 0, especially, tetraalkoxysilanes are preferred. Tetraalkoxysilane or tetra
The use of partial hydrolysis products of alkoxy silanes, first
Excellent in compatibility with layer and adhesion. Of course , a favorable second layer can be formed by using this compound in combination with another silane compound or by adding an additive component described later.

[0055] While specific examples of the compound (C) below, the compound (C) is Lena have limited thereto.

[0056] tetramethoxysilane, tetraethoxysilane, tetra (n- propoxy) silane, Tet Raiso flop <br/> Ropoki shish run, tetra (n- butoxy) silane, tetra (sec-butoxy) silane, tetra (t- Tetraalkoxysilanes such as butoxy) silane.

[0057] methyltrimethoxysilane, methyltriethoxysilane, et triethoxysilane, vinyl trimethoxysilane, phenyl triethoxysilane, .gamma.-chloropropyl trimethoxy silane, .gamma.-chloropropyltriethoxysilane, 3,3,3 -Trifluoropropyltrimethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane,

[0058] .gamma. methacrylic acryloyloxy propyl trimethoxy silane, .gamma.-mercaptopropyltrimethoxysilane, .gamma.-mercaptopropyl triethoxysilane, gamma
- aminopropyltrimethoxysilane, .gamma.-aminopropyltriethoxysilane, N-(beta - A Minoechiru) -
γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane,

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-
Trialkoxysilanes such as (3,4-epoxycyclohexyl) butyltrimethoxysilane and δ- (3,4-epoxycyclohexyl) butyltriethoxysilane.

Methyltriacetoxysilane, vinyltriacetoxysilane, phenyltriacetoxysilane, γ
- tri scan such chloropropyl triacetoxysilane
( Acyloxy ) silanes.

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

[0065] 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.

[0070] In the present invention, the first layer is the outermost layer of the surface treatment layer, a fluorine-containing organosilane compounds (I) also <br/> is a layer obtained by treatment with the partial hydrolysis products. The treatment agent for forming the layer, a treatment agent containing fluorine organosilane compound (I) or containing a partial hydrolysis product, preferably particularly for use as a solution or dispersion. The said treatment agent, in addition to a solvent or a dispersant, wear still other additives added pressure.

[0071] As the added vulcanizing agent include acid for performing pressurized hydrolysis. Further, the hydrolyzable silane compound (II) or its partial hydrolysis products also kills with added addition to the treatment agent. The addition amount, particularly LIMITED Lena Iga, fluorinated organosilane compound (I) and an equal weight or less are preferred with respect to the sum of its partial hydrolysis product, preferably particularly 50 wt% or less.

[0072] The further processing may include silica, fine particles include metal oxides such as aluminum oxide or zirconium oxide, ultrafine particles is preferably in the sol, such as particularly silica sol and Ariminazoru, other filler component, epoxy resin , unsaturated polyester resins, polyurethane resins, or (meth) binder component, such as acrylates or the like can be used. The surfactant to enhance film-forming treatment agent (workability) also cut with added pressure.

The amount of the additional components other than the solvent and the dispersant in the treating agent can be changed according to the purpose, but usually , the amount is preferably 40 parts by weight or less based on 100 parts by weight of the total silane compound.
And particularly preferably 10 parts by weight or less. When a filler component is used as an additive, the amount is preferably 0.1 to 20 parts by weight.
And particularly preferably 1 to 10 parts by weight. When a binder component is used, the content is preferably 10 parts by weight or less, particularly 0.5 part by weight.
-5 parts by weight is preferred. Excessive addition of these additives,
It is not desirable because it lowers water repellency, abrasion resistance and the like.

[0074] treatment agent on the substrate surface to be coated object, straight <br/> contact may be applied by a method such as hand wiping. Also, the treatment agent
The solution also can be used in the form of the dispersion is preferred for reasons such as coating workability. In solution or dispersion according to the organic solvent or the like, the total amount of coating forming (workability) of the total silane compounds contained, stability, coating thickness is determined in consideration of economy, 0.1 to 30 Preferably, it is weight%.

[0075] acid esters as organic solvent, aromatic hydrocarbons, halogenated hydrocarbons, ketones, or various solvents such as <br/> ethers you can use. The solvent is not limited to one type, and it is also possible to use a mixture of two or more types.

[0076] a lower layer in contact with the outermost layer and the second layer含Fu
Tetraalkoxy other than nitrogen organosilane compound (I)
Shishiran or a layer obtained by treating with a treating agent comprising a partial hydrolysis product. Processing for forming the second layer
The management agent, Tetoraaruko Kishishiran or containing the partial hydrolysis product, a solution or dispersion is preferred.
The said treatment agent, in addition to a solvent or dispersing agent can be further added other additives. Solvent, dispersing agent, the like other additives, can be used the same as described above, also, it is preferable that the amount of usage is also according to the above. Of course , this second
Treatment agent for forming the layers, the fluorine-containing organosilane compound (I) or a treatment agent which does not substantially contain a partial hydrolysis product.

[0077] also surface treatment of the substrate when the surface treatment for forming the first layer to the second layer surface, no special pretreatment is unnecessary. However, the line also by <br/> rather pretreatment according to the purpose, for example, hydrofluoric acid diluted acid treatment with hydrochloric acid, sodium hydroxide, alkali treatment with aqueous potassium hydroxide and the like, or plasma irradiation Discharge treatment, etc.
Is Ru.

[0078] formation of each layer, the prepared treatment agent to the substrate surface by conventional processing methods, brushing, flow coating, rotary coating, applied by various methods such as dip coating or spray coating, in air or nitrogen Motochu, method or drying by heating at normal temperature is preferred. Further, in the case of conducting the firing
The under drying temperature or preferred that further heating to a high temperature
New When heated in consideration of the heat resistance of the substrate, the temperature, it is preferable to set the time.

The thickness of each layer to be formed can be appropriately controlled by the concentration of the treatment agent , the application conditions, the heating conditions, and the like. 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, in order to exhibit water repellency, it is theoretically necessary that the thickness of the film be a monolayer or more, and 2 μm in consideration of the economic effect.
m or less.

[0080] In the front surface treated substrate, it is difficult to adhere repelled water drops attached to the surface by the water repellency, even if the deposition amount is small be attached, also it is easy to remove the adhered water drops . 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.

[0081]

EXAMPLES Hereinafter, illustratively describes the present invention examples, but the invention is Lena have limited to the examples. All in Example
It was carried out in various evaluations Hatsu skills of how.

1. Water repellency (1 ) The contact angle to water was measured. The measurement is performed at five different locations on the substrate surface, and the average value is shown. (2 ) After spraying water over the entire surface for about 1 hour from a nozzle held at a distance of 20 cm from the sample surface, water droplets remaining on the surface were visually observed and evaluated according to the following evaluation criteria.

A: No water remains on the sample surface. B: Some water remains on the sample surface. C: 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. A wear resistance test was performed by the above method, and the water repellency after the test was evaluated.

3. Weathering test UV irradiation was performed for 8 hours (70 ° C) and wet exposure was performed for 4 hours (5 hours).
The 0 ° C.) to process as one cycle, 100 cycles
It was to evaluate the water repellency after the actual applied.

[0086] 4. Boiling test The water repellency after immersion in boiling water for 1 hour was evaluated.

5. Compound used (a) (CH ₃ O) ₃ SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (OCH ₃ ) ₃ (b) (CH ₃ O) ₂ (CH ₃ ) SiC ₂ H ₄ C ₆ F ₁₂ C ₂ H ₄ Si (CH ₃ ) (OCH ₃ ) ₂ (c) C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ (d) Si (OCH ₃ ) ₄ (e) Epoxy resin (trade name “EP827 , Yuka Shell Epoxy Co., Ltd.) (f) Methanol-dispersed silica sol (solid content 30% by weight,
Catalyst Chemicals Co., Ltd.)

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

[0089] In the treatment agent 2 Preparation] stirrer and thermometer is set flask, (d)
75.0 g, (f) 10.9 g, methyl alcohol 12
33.5 g and 2000.0 g of isopropyl alcohol were 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 completion of the dropwise addition, the liquid temperature and stirring was continued for 5 days while kept at 25 ° C., to obtain a treating agent 2.

[0090] In the treating agent Preparation of 3] stirrer and thermometer is set flask, (a)
56.3 g, (c) 29.4 g and (d) 43.9 g were mixed, 1531.9 g of methyl alcohol and 7000.0 g of isopropyl alcohol were added, and 8.9 g of sodium acetate was further added, followed by stirring for 1 hour. While maintaining the temperature of the solution at 5 ° C., 34.5 g of a 1% aqueous hydrochloric acid solution was gradually added dropwise. After completion of the dropwise addition, the liquid temperature and stirring was continued for 5 days while kept at 25 ° C., to obtain a treating agent 3.

[0091] In the preparation of the treatment agent 4] stirrer and thermometer is set flask, (a)
23.0 g, (b) 10.8 g, (c) 30.0 g,
Mixing (d) 22.4 g and (e) 13.6 g,
1708.9 g of methyl alcohol and 7000.0 g of isopropyl alcohol were added, and the mixture was stirred for 1 hour. While maintaining the temperature of this solution at 5 ° C, 13.6% aqueous hydrochloric acid solution 23.6.
g was slowly added dropwise. After completion of the dropwise addition, the liquid temperature and stirring was continued for 5 days while kept at 25 ° C., to obtain a treating agent 4.

Example 1 A glass plate having a size of 10 cm × 10 cm (thickness: 3 mm) was immersed in a solution of the treating agent 1 and pulled up at a speed of 11 cm / min.
Heated at 80 ° C. for 10 minutes. This test specimen was placed at room temperature for 30 minutes.
After leaving for 3 minutes, it is immersed in the solution of the treating agent 3 and 11 cm / min.
, And heated at 200 ° C. for 30 minutes to prepare a sample test piece. Table 1 shows the evaluation results of the test pieces.
Shown in

Example 2 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 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 1 in Example 1 was changed to the treating agent 2. The results are shown in Table 1.

Example 4 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 5 The heating after the immersion of the treating agent 1 in Example 1 was carried out at 80 ° C. for 1 hour .
The test and evaluation were performed in the same manner as in Example 1 except that the temperature was changed from 0 minutes to 300 ° C. for 30 minutes. The results are shown in Table 1.

Comparative Example 1 A glass plate having a size of 10 cm × 10 cm (thickness: 3 mm) was immersed in a solution of the treating agent 3 and pulled up at a speed of 11 cm / min.
Sample test pieces were prepared. Table 1 shows the results of evaluating the test pieces.

[0098]

[Table 1]

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

[0100]

[Table 2]

Example 7 A coating was formed on the surface of an architectural glass plate by the method of Example 1 to form a coating . The obtained architectural glass plate was mounted on a building. This windowpane was exposed for one month ,
The state of adhesion of dirt and dust on the surface of the window glass and the state of adhesion of water drops in rainy weather were visually observed. As a result, dirt, dust adhesion of the generation of fur due to attachment of the water droplets was not observed at all, rarely <br/> is readily divided removed by wiping gently with a tee Tsu tissue paper also their occurrence is observed Came.

The time and effort for cleaning the window glass could be greatly simplified. Also, in rainy weather, water droplets on the surface were repelled and there was no spreading of water, making it easy to secure a visual field. In addition, on rainy days and on windy days, water droplets move quickly due to interaction with wind pressure, making it easier to secure a visual field.

[0103] Further, water droplets freezing attached to the window glass of the untreated, or exposure in an environment such that icing the window glass condense moisture in the air (0 ℃ ~-5 ℃) No icing on the window glass surface was observed in the test. Moreover , in a severer low temperature environment (-10 ° C ~
At −15 ° C.), icing on the window glass was also observed, but the thawing due to the temperature rise was fast and there was a significant difference compared to untreated window glass.

Example 8 An exposure test was performed by changing the architectural glass plate of Example 7 to a heat ray reflective glass plate for architectural use (“Sunlux SS8” manufactured by Asahi Glass Co., Ltd.). As a result, the same effect as in Example 7 was confirmed.

[0105]

The construction and construction base material and construction and construction article of the present invention have excellent effects as described in the examples. That is, 1. Excellent in water repellency, dust, dirt, adhesion of water drops,
Or no such occurrence of fur due to it, rarely even their generation, can be easily removed, it is possible to block the adverse effects of water-induced, also simplification of cleaning can be achieved.

2. It has excellent water repellency and maintains its state semipermanently. 3. It has excellent chemical resistance and is effective when used along the coastline. 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.

Continuation of the front page (56) References JP-A-60-95433 (JP, A) JP-A-61-274766 (JP, A) JP-A-62-277182 (JP, A) JP-A-2-107380 (JP) JP-A-2-173174 (JP, A) JP-A-4-74572 (JP, A) JP-A-4-219174 (JP, A) JP-A-3-115479 (JP, A) 2-16186 (JP, A) JP-B 61-5667 (JP, B2) JP-B 1-20658 (JP, B2) JP-B 5-500327 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) B05D 7/24 302 B05D 7/00 C09K 3/18 104 C03C 25/40

Claims (8)

(57) [Claims] Consisting treated substrate having at least two treated surface layers to 1. A substrate surface, or as a component of the treated substrate, a building and construction wearing article, the surface treatment layer top resulting fluorinated organosilane compound having an organic group and a hydrolyzable group first layer is the outer layer has two or more fluorine atoms (I) or by treatment with a treating agent comprising a partial hydrolysis product A second layer, which is a lower layer in contact with the outermost layer, is made of a material other than the fluorine-containing organosilane compound (I) .
Tetraalkoxysilane or partial hydrolysis products thereof
Architectural and architectural articles which are layers obtained by treating with a treating agent containing: 2. The tetraalkoxysilane as tetoxysilane
The building according to claim 1, wherein only lamethoxysilane is used.
・ Building articles. 3. The method according to claim 1, wherein the fluorine-containing organosilane compound (I) is,
The following formula (A)Compound represented byOrThe following formulaIn (B)
tableI2. The compound according to claim 1,Or described in 2Building
Construction and construction goods. (A) X_3-ab(R¹)_a(R^Two)_bSi-Y-Si (R^Three)_c(R^Four)_dX_3-cd Wherein X is a hydrolyzable group, R¹ , R^Two , R^Three ,and
R^Four Independently,hydrogenatomOr 1 carbon~16 organic
Group, aandb is independently,0, 1,Or2Rikatsu
An integer satisfying 0 ≦ a + b ≦ 2, candd is independent,
0, 1,Or2RikatsuInteger satisfying 0 ≦ c + d ≦ 2
number, YIs 2WorthRepresents a machine, Y orIs R ¹~ R^Four Little
At least oneIsAn organic group having two or more fluorine atoms
is there. (B)(R _f ) _e (R ^Five ) _g (R ⁶ ) _h SiX _4-egh  Wherein X is a hydrolyzable group, R_f Is two or more fluorine atoms
An organic group having^Five andR⁶ Independently,hydrogenatomMa
Or 1 carbon~16 organic groups, e is 1, 2,Or3,
gandh is independent,0, 1, 2,Or3Rikatsu
Represents an integer satisfying 1 ≦ e + g + h ≦ 3. 4. The method according to claim 1, wherein the fluorine-containing organosilane compound (I) is
Divalent Contact Keru Y in formula (A) has two or more fluorine atoms
Organic compounds is a group, R ¹ in formula (A), R ^2, R
³ and R ⁴ At least one organic group Der Ru compound having 3 or more polyfluoroalkyl group carbon of, also
Claim the compound is an organic radical Contact Keru R _f in the formula (B) has a number of 3 or more polyfluoroalkyl group carbon,
3. The article for construction and construction according to 3 . 5. The method according to claim 1 , wherein the second layer is formed of a tetraalkoxysilane.
Or silica sol with its partial hydrolysis products
A layer obtained by treating with a treating agent.
Or the architectural / building article according to 4. 6. The thickness of the first layer is from a monolayer thickness to 2 μm.
The thickness of the second layer is from a monolayer thickness to 20 μm.
Item 6. The article for construction and construction according to any one of Items 1 to 5. 7. Any substrate is 請 Motomeko 1-6 Ru glass der
The building / building article described in the crab . 8. The surface of an architectural / building article base material is fluorine-containing.
Tetraalkoxy compounds other than organosilane compound (I)
A second layer is formed by treating with a treating agent containing a run or a partial hydrolysis product thereof , and then the surface of the second layer is coated with a fluorine-containing organosilane compound (I) or a partial hydrolysis product thereof.
Forming a first layer is treated with a treating agent comprising a front surface treatment layer
Manufacturing method of architectural and construction wearing article to be.