JP5131840B2 - COATING COMPOSITION AND HIGH DRILLING FILM USING THE COMPOSITION - Google Patents

Description

  The present invention particularly provides a coating agent composition that imparts water and oil repellency and high water slidability to the surface of window glass of automobiles, trains, ships, aircraft, etc., window glass of high-rise buildings, sanitary ware, and the like, and the composition It is related with the membrane | film | coat using.

  In general, a perfluoropolyether group-containing compound has chemical resistance, lubricity, releasability, water and oil repellency, and the like. Utilizing its properties, it is widely used for magnetic recording medium lubricants, precision equipment oilproofing agents, mold release agents, water / oil repellent and antifouling agents such as paper and fiber, cosmetics, and protective films.

  On the other hand, silane coupling agents are well known as coating agents for glass, ceramics, resin films, cloths and the like. The silane coupling agent has an organic functional group and a reactive silyl group (generally an alkoxysilyl group) in one molecule. The alkoxysilyl group is hydrolyzed by moisture in the air and the like, and undergoes a self-condensation reaction to form a siloxane to form a film. At the same time, a strong and durable coating is obtained by chemically and physically bonding to the surface of glass or resin. Silane coupling agents are widely used as coating agents for various substrate surfaces using this property.

  A glass using a fluoroalkyl group-containing silane compound that places importance on the durability of water repellency can maintain water repellency for a long period of time, but has poor lubricity and a problem with water droplet removal (see Patent Document 1). The ease of removing water droplets can be evaluated by the water falling angle, that is, the inclination angle at which 10 μl of water droplets are placed on a flat surface, and then the flat surface is gradually inclined so that the water droplets begin to slide down.

  In the use of window glass for vehicles, a water-slidable coating made of a copolymer of fluoroalkyltrichlorosilane and silanol-terminated dimethylsiloxane has been proposed (Patent Document 2). Although the initial water repellency is about 100 degrees, it becomes 100 degrees or less after wear, and there is a problem in durability.

  In addition, glass using a perfluoroether group-containing silane compound (Patent Document 3) with an emphasis on oil repellency has good water and oil repellency, and is less susceptible to oil stains and can be easily wiped off. However, the water sliding angle was not less than 10 degrees in terms of water slidability.

It is desirable that the glass surface of automobiles, trains, ships, aircraft, skyscrapers, etc. has a low water fall angle. In the case of a surface with a low water tumbling angle, sometimes referred to as a “highly slidable surface”, even if water droplets adhere to the surface, the water drops naturally or is easily removed by the wind. Can be shortened. Further, if the surface is oil-repellent, it can be easily wiped even if excrement such as oil, insects and animals adheres. Also, in applications such as sanitary ware, sinks, kitchenware, and sewage pipes, it is required to have a performance that is difficult to get dirty and easy to wipe away, and it is desirable to make the surface water and oil repellant.
JP 10-59745 A Japanese Patent Laid-Open No. 2002-12453 JP 2003-238777 A

  The present invention is excellent in water and oil repellency and water slidability, and can further maintain these performances over a long period of time. Specifically, the water repellency angle is 100 degrees or more, the oil repellency angle is 60 degrees or more, It is an object of the present invention to provide a coating agent capable of forming a film having a sliding angle of less than 10 degrees and a small decrease in performance due to wear.

  As a result of intensive studies, the inventor has found that an inorganic oxide such as silicon dioxide can be obtained using a treatment agent mainly composed of a perfluoropolyether-polysiloxane copolymer-modified silane represented by the following formula (1). The coating obtained by treating the coated film or glass surface can simultaneously satisfy the water slidability of the siloxane while retaining the water and oil repellency and high durability characteristics of the perfluoropolyether-modified silane. As a result, the present invention has been made.

［式中、Ｚは−（Ｍｅ_２ＳｉＯ）_ｘＭｅ_２Ｓｉ−で表される（式中、Ｍｅはメチル基を意味し、ｘは１〜４０の整数である）２価のポリオルガノシロキサン残基、Ｒは炭素数１〜４のアルキル基またはフェニル基、Ｘは互いに異なっていてよい加水分解性基、Ｑはアミド、エーテル、エステル、又はアルキレン結合を含む炭素数２〜１２の２価の連結基、ａは２又は３、ｂは１の整数、ｙは１〜５の整数であり、Ｒｆは下記式（２）で示される基
−Ｒｆ^１−（Ｑ−Ｗ−Ｑ−Ｒｆ¹）_ｑ− （２）
（式中、Ｒｆ^１はパーフルオロポリエーテル残基、Ｗは下記式（７）又は（８）で示される基であり、

（式中、ｇは１〜４０の整数であり、Ｒ^′は同一または異なってもよい炭素数１〜４のアルキル基又はフェニル基である。）

（式中、ｙは１〜５の整数、ｈおよびｉは夫々１〜４０の整数、但し、ｈ＋ｉは２〜４０であり、Ｒ^′は上述のとおりである）
及びＱは上記と同様の基であり、それぞれ同じでも異なってもよく、ｑは０〜３の整数である。）］及び
アルコール、エステル、エーテル、ケトン、及びパーフルオロエーテルからなる群より選ばれる少なくとも一種の溶剤、
を含むコーティング剤組成物である。
That is, the present invention provides a fluorine-containing silicon compound represented by the following formula (1):

[Wherein Z is represented by-(Me ₂ SiO) _x Me ₂ Si- (wherein Me represents a methyl group and x is an integer of 1 to 40), a divalent polyorganosiloxane residue. Group, R is an alkyl group having 1 to 4 carbon atoms or phenyl group, X is a hydrolyzable group which may be different from each other, Q is an amide, ether, ester, or divalent divalent having 2 to 12 carbon atoms including an alkylene bond Linking group, a is 2 or 3, b is an integer of 1 , y is an integer of 1 to 5, and Rf is a group represented by the following formula (2) -Rf ^1- (QWQ-Rf ¹ ) _q − (2)
(In the formula, Rf ¹ is a perfluoropolyether residue, W is a group represented by the following formula (7) or (8),

(In the formula, g is an integer of 1 to 40, and R ^' is the same or different alkyl group having 1 to 4 carbon atoms or phenyl group.)

(Wherein y is an integer of 1 to 5, h and i are each an integer of 1 to 40, provided that h + i is 2 to 40 and R ^' is as described above)
And Q are the same groups as described above, and may be the same or different, and q is an integer of 0 to 3. )] And at least one solvent selected from the group consisting of alcohols, esters, ethers, ketones, and perfluoroethers,
It is a coating agent composition containing this.

  The coating obtained from the coating composition of the present invention is not only easy to wipe off with water and oily stains, but also has the above characteristics for a long time because both ends of the fluorine-containing silicon compound are firmly adhered to the substrate. it can.

  A fluorine-containing silicon compound represented by the following formula (1):

は、加水分解性基Ｘを含む。従って、該化合物には、Ｘが加水分解したもの、及び、該加水分解物が互いに縮合した縮合物の形態ものも包含される。

Contains a hydrolyzable group X. Therefore, the compound includes a product obtained by hydrolyzing X and a product obtained by condensing the hydrolyzate with each other.

In the formula (1), Rf is a group represented by the following average composition formula (2).
^{-Rf 1 - (Q-W-} Q-Rf 1) q - (2)
In which Rf ¹ is a perfluoropolyether residue, W is branched and may have a silalkylene group, a polyorganosiloxane residue having 1 to 40 siloxane units, and Q Are the same groups as described above, and may be the same or different, and q is an integer of 0 to 3.

Here, it does not matter whether Rf ¹ is linear or branched. The perfluoropolyether structure includes a repeating unit of —C _j F _2j O— (wherein j of each unit is an integer of 1 to 6). _j F _2j O) _k - with like those shown. Here, k is an integer of 1 to 500, preferably 2 to 400, more preferably 10 to 200.

Examples of the repeating unit —C _j F _2j O— represented by the above formula include the following units. In addition, the said perfluoroalkyl ether structure may be comprised by 1 type of these repeating units individually, and the combination of 2 or more types may be sufficient as it.
—CF ₂ O—
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-
_{-CF 2 CF 2 CF 2 CF 2} O-
_{-CF 2 CF 2 CF 2 CF 2} CF 2 CF 2 O-
-C _{(CF 3)} 2 O-

In particular, it is a perfluoropolyether having a perfluoroether group having about 1 to 4 carbon atoms represented by the following units as a repeating unit.
—CF ₂ O—
-CF ₂ CF ₂ O-
-CF ₂ CF ₂ CF ₂ O-
-CF (CF ₃ ) CF ₂ O-

In the above formula (1), the divalent perfluoroether-containing group Rf ¹ is preferably selected from the groups represented by the following general formulas (3), (4) and (5).

（式中、Ｙはそれぞれ独立にＦ又はＣＦ_３基、ｒは２〜６の整数、ｄは１〜３の整数、ｍ、ｎはそれぞれ０〜２００の整数で、ｍ＋ｎ＝２〜２００、ｓは０〜６の整数である。該一般式中の繰り返し単位の配列はランダムである。）

(Wherein Y is independently F or CF ₃ group, r is an integer of 2 to 6, d is an integer of 1 to 3, m and n are integers of 0 to 200, and m + n = 2 to 200, s Is an integer of 0 to 6. The arrangement of repeating units in the general formula is random.)

（式中、ｌは１〜２００の整数、ｄは１〜３の整数である。）

(In the formula, l is an integer of 1 to 200, and d is an integer of 1 to 3.)

（式中、ＹはＦ又はＣＦ_３基、ｄは１〜３の整数、ｍ、ｎはそれぞれ０〜２００の整数で、ｍ＋ｎ＝２〜２００である。該一般式中の繰り返し単位の配列はランダムである。）

(In the formula, Y is F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, and m + n = 2 to 200. The arrangement of repeating units in the general formula is Random.)

The total number of repeating units in the chemical structural formula is preferably 1 to 60, more preferably 10 to 50.

Further, in the formula (2), it is preferable that Rf ¹ is a perfluoropolyether-containing group represented by the following general formula (6) in terms of good antifouling properties and good wear resistance.
_{-CF 2 (OC 2 F 4)} e (OCF 2) f OCF 2 - (6)
(In the formula, e = 0 to 50, f = 1 to 50 and e + f = 2 to 60 are integers.)

In formula (I), Q may contain oxygen and / or nitrogen, a divalent group linking Rf group and Z group, Rf ¹ and Z, the Rf ¹ and W, amide, ether, ester, alkylene linkages And the like.

  For example, the following groups are mentioned.

In the above formula (1), Z is represented by- (Me ₂ SiO) _x Me ₂ Si- (wherein Me represents a methyl group, x is an integer of 1 to 40) , siloxane unit 1 It is a divalent polyorganosiloxane residue having ˜40. When there is no Z, when Z is trivalent or more, or when the siloxane unit exceeds 40, the water falling angle tends to exceed 10 degrees.

  Examples of Z include the following.

In the above formula (2), W is a polyorganosiloxane residue having 1 to 40 siloxane units which may have a branch and may have a silalkylene group. When the number of siloxane units exceeds 40, the water falling angle tends to exceed 10 degrees. Examples of the polysiloxane residue include groups represented by the following formula (7) or (8). Here, R ^' is the same or different C1-C4 alkyl group or phenyl group.

ここで、ｇは１〜４０の整数である。Ｒ^′は同一または異なってもよい炭素数１〜４のアルキル基又はフェニル基である。

Here, g is an integer of 1-40. R ^' is the same or different C1-C4 alkyl group or phenyl group.

ここで、ｙは１〜５の整数、ｈおよびｉは夫々１〜４０の整数、但し、ｈ＋ｉは１〜４０であり、Ｒ^′は上記と同じである。
式（７）、（８）で表される残基として、例えば下記のものがあげられる。

Here, y is an integer of 1 to 5, h and i are each an integer of 1 to 40, where h + i is 1 to 40, and R ^' is the same as above.
Examples of the residues represented by the formulas (7) and (8) include the following.

ここで、Ｍｅはメチル基、Ｅｔはエチル基、Ｐｈはフェニル基を示す。

Here, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group.

  In formula (1), X represents a hydrolyzable group and has one or more at the terminal, but may be the same or different. Specific examples thereof include alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, oxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy group and methoxyethoxy group, and acetoxy groups. And an alkenyloxy group having 2 to 10 carbon atoms such as an acyloxy group having 1 to 10 carbon atoms and an isopropenoxy group, a halogen group such as chloro group, bromo group and iodo group. Of these, a methoxy group, an ethoxy group, an isopropenoxy group, and a chloro group are preferable.

  R is a lower alkyl group having 1 to 4 carbon atoms or a phenyl group, specifically a methyl group, an ethyl group, a phenyl group, or the like. Among them, a methyl group is preferable. a is 2 or 3, and 3 is preferable from the viewpoint of reactivity and adhesion to a substrate. b is 1-10, and 1-5 is preferable from the coexistence of the adhesiveness to a base material, and antifouling performance.

  The coating agent composition of the present invention contains a solvent or diluent. Examples of such solvents include alcohols (ethyl alcohol, isopropyl alcohol, etc.), hydrocarbon solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.), ester solvents (ethyl acetate, isopropyl acetate, butyl acetate, etc.) ), Ether solvents (diethyl ether, isopropyl ether, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), and polar solvents such as alcohols, esters, ethers, ketones are preferably used and dissolved. Isopropyl alcohol and methyl isobutyl ketone are particularly preferred from the viewpoints of water property, wettability and safety. Fluorinated solvents are also preferably used. Examples thereof include fluorinated aliphatic hydrocarbon solvents (perfluoroheptane, etc.), fluorinated aromatic hydrocarbon solvents (m-xylene hexafluoride, benzotrifluoride, etc.). And fluorinated ether solvents [methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), ethyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, etc.]. Among them, in terms of solubility and wettability, A fluoro solvent is desirable, and a perfluoro ether solvent is particularly preferably used.

  In addition, the said solvent may be used individually by 1 type, or may be made to mix 2 or more types, In any case, it is preferable to use what dissolves the said component uniformly.

  The amount of the solvent used is not particularly limited, and the optimum concentration varies depending on the treatment method, but the solid content in the composition is 0.05 to 1% by mass, particularly 0.1 to 0.3% by mass. It is preferred to use an amount. Solid content means the mass of a non-volatile component, and when a composition contains the curing catalyst etc. which are mentioned later, it will be the compound of Formula (1), and those total mass.

  It is preferable to add a curing catalyst to the coating composition as necessary. Organic titanate ester, organotitanium chelate compound, organoaluminum compound, organozirconium compound, organotin compound, metal salt of organic carboxylic acid, amine compound and its salt, quaternary ammonium compound, lower fatty acid salt of alkali metal, dialkylhydroxy Examples include amines, guanidine group-containing organosilicon compounds, inorganic acids, perfluorocarboxylic acids, perfluoroalcohols, and the like, and preferably perfluorocarboxylic acids are used.

  The addition amount of the curing catalyst is a catalytic amount, 0.05 to 5 parts by mass, particularly 0.1 to 1 part by mass with respect to 100 parts by mass of the fluorine-containing silicon compound of the present invention and / or its partial hydrolysis condensate. Preferably there is.

  As a method for applying the coating agent composition thus obtained to a substrate, there are known methods such as brushing, dipping, spraying and vapor deposition.

  Further, the processing temperature of the applied coating agent varies depending on the application method. For example, in the case of brush coating or dipping, a temperature range of room temperature to 40 ° C. is desirable. As the treatment humidity, it is desirable to perform the treatment under humidification in order to promote the reaction. In addition, it is desirable to optimize the said process conditions suitably according to a material, a curing catalyst, etc.

  The substrate to be treated with the above coating agent is not particularly limited, but as the substrate, an inorganic oxide layer, a metal oxide layer, a hard coat layer, a silane coupling formed on the surface of an organic substance such as ceramics, glass, film, etc. Various materials such as a layer can be used. Examples of the water / oil repellent treatment include paper, cloth, metal, glass, plastic, and ceramic.

  Although the film thickness of the cured film formed on the various base materials or article surfaces is appropriately selected depending on the type of the base material, it is 1 nm to 50 nm, preferably 3 nm to 20 nm.

  The resulting coating is not only water and oil repellent but also highly lubricious. In the present invention, the water slidability was evaluated by the falling angle of water as described later. Such characteristics are effective for applications that are often exposed to water and are not easily maintained, such as oils and fats, fingerprints, cosmetics, sunscreen cream, human and animal excrement, oils, etc. Window glass for trains, ships, aircraft, etc., window glass for high-rise buildings, head lamp covers, outdoor equipment, telephone boxes, outdoor large displays, sanitary products such as bathtubs, washstands, electric razors, makeup tools, kitchens Building materials, water tanks, medical equipment and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by this.

[Examples 1 to 6]
Compounds 1-6 are each dissolved in HFE-7200 (manufactured by Sumitomo 3M) to prepare a 0.2 wt% solution, and 0.2 wt% perfluorocarboxylic acid is added to the solid content. A coating agent composition was prepared. The slide glass was immersed in each composition for 10 seconds and then pulled up at a speed of 150 mm / min, and allowed to stand in an atmosphere at room temperature (25 ° C., humidity 40%) for 24 hours to form a cured film.

[Comparative Examples 1-5]
Compounds 7 to 11 are dissolved in HFE-7200 (ethyl perfluorobutyl ether, manufactured by Sumitomo 3M) to prepare a 0.2 wt% solution, and 0.2 wt% of the solid content is added to the solution. Fluorocarboxylic acid was added to prepare a coating composition. The slide glass was immersed in the treatment agent for 10 seconds, then pulled up at a speed of 150 mm / min, and allowed to stand in an atmosphere at room temperature (25 ° C., humidity 40%) for 24 hours to form a cured film.

The obtained cured film was evaluated by the following test method.
[Water and oil repellency]
Using a contact angle meter (A3 type, manufactured by Kyowa Interface Science Co., Ltd.), the water contact angle of the cured film and the contact angle with respect to oleic acid were measured.
[Water drop angle]
Using a contact angle meter (A3 type, manufactured by Kyowa Interface Science Co., Ltd.), the drop angle of water droplets (10 μl) on the surface of the cured film was measured.

[Abrasion test]
Using a rubbing tester (manufactured by Shinto Kagaku Co., Ltd.), a rubbing test using a nonwoven fabric was performed under the following conditions to evaluate the wear resistance. 8 sheets of non-woven fabric (cotton) were wrapped and wrapped around the tip (1.5 cm × 1.5 cm) of the tester in contact with the sample, fixed with a rubber band, and used as a rubbing material.
Evaluation environmental conditions: 25 ° C, humidity 40%
Travel distance (one way) 4cm:
Travel speed 500cm / min:
Load: 1kg
Number of rubbing: 6000 times [Compound 1]

［化合物２］

[Compound 2]

［化合物３］

[Compound 3]

［化合物４］

[Compound 4]

［化合物５］

[Compound 5]

［化合物６］

[Compound 6]

［化合物７］

[Compound 7]

［化合物８］

[Compound 8]

（ｐ／ｑ＝０．９ ｐ＋ｑ≒４５）

［化合物９］

(P / q = 0.9 p + q≈45)

[Compound 9]

（ｐ／ｑ＝０．９ ｐ＋ｑ≒４５）

［化合物１０］

(P / q = 0.9 p + q≈45)

[Compound 10]

［化合物１１］

[Compound 11]

上記式において、ｐ＋ｑの値は平均値である。

In the above formula, the value of p + q is an average value.

  The evaluation results are shown in Table 1.

  In Examples 1 to 6 and Comparative Examples 1 to 5, the initial water contact angle was 100 degrees or more and the oleic acid contact angle was 60 degrees or more, which were excellent water and oil repellent surfaces. On the other hand, the water falling angle was less than 10 degrees in the examples, and showed excellent water slidability. Moreover, the water falling angle of less than 10 degrees was maintained even after the abrasion test. In Comparative Examples 1 and 2 that do not have Z and Comparative Example 3 in which Z is trivalent, the water falling angle exceeded 10 degrees. In Comparative Examples 4 and 5 in which the number of siloxane units corresponding to Z or W exceeds 40, the water falling angle exceeded 10 degrees.

Claims (10)

A fluorine-containing silicon compound represented by the following formula (1):

[Wherein Z is represented by-(Me ₂ SiO) _x Me ₂ Si- (wherein Me represents a methyl group and x is an integer of 1 to 40), a divalent polyorganosiloxane residue. Group, R is an alkyl group having 1 to 4 carbon atoms or phenyl group, X is a hydrolyzable group which may be different from each other, Q is an amide, ether, ester, or divalent divalent having 2 to 12 carbon atoms including an alkylene bond Linking group, a is 2 or 3, b is an integer of 1 , y is an integer of 1 to 5, and Rf is a group represented by the following formula (2) -Rf ^1- (QWQ-Rf ¹ ) _q − (2)
(In the formula, Rf ¹ is a perfluoropolyether residue, W is a group represented by the following formula (7) or (8),

(In the formula, g is an integer of 1 to 40, and R ^' is the same or different alkyl group having 1 to 4 carbon atoms or phenyl group.)

(Wherein y is an integer of 1 to 5, h and i are each an integer of 1 to 40, provided that h + i is 2 to 40 and R ^' is as described above)
And Q are the same groups as described above, and may be the same or different, and q is an integer of 0 to 3. )] And at least one solvent selected from the group consisting of alcohols, esters, ethers, ketones, and perfluoroethers,
A coating agent composition comprising:   The composition of Claim 1 whose density | concentration of a fluorine-containing silicon compound is 0.05-1 mass%. In the formula (2), Rf ¹ is represented by the following formula (3), (4) or (5) represented by the composition according to claim 1 or 2.

(Wherein Y is independently F or CF ₃ group, r is an integer of 2 to 6, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, m + n is 2 to 200, and s is An integer of 0 to 6, and the sequence of each repeating unit in the formula may be random)

(In the formula, l is an integer of 1 to 200, and d is an integer of 1 to 3.)

(Wherein Y is F or CF ₃ group, d is an integer of 1 to 3, m and n are each an integer of 0 to 200, provided that m + n is 2 to 200, and the arrangement of each repeating unit in the formula is random. May be) The composition according to any one of claims 1 to 3, wherein Rf ¹ is represented by the following formula (6) in the formula (2).
_{-CF 2 (OC 2 F 4)} e (OCF 2) f OCF 2 - (6)
(In the formula, e is 0 to 50, f is an integer of 1 to 50, and e + f is an integer of 2 to 60.) The composition according to any one of claims 1 to 4, wherein x in formula (1) is an integer of 1 to 21.   The composition according to any one of claims 1 to 5, wherein the hydrolyzable group X is an alkoxy group.   The composition according to any one of claims 1 to 6, wherein in the formula (1), Q is any group represented by the following formula.

The composition according to any one of claims 1 to 7 , further comprising a curing catalyst. An article provided on its surface with a cured film obtained from the composition according to any one of claims 1 to 8 . A method for imparting water slidability to the surface of an article comprising the following steps: (1) A step of applying the composition according to any one of claims 1 to 8 to the surface of the article;
(2) A step of curing the applied composition at room temperature.