JP4998723B2 - Fluorine-containing coating agent composition - Google Patents

Description

  The present invention mainly comprises a perfluoropolyether-polysiloxane copolymer-modified silane that is excellent in lubricity, water repellency, oil repellency, solvent resistance, chemical resistance, and weather resistance and can be cured at room temperature or by heating. The present invention relates to a water / oil repellent coating composition as a component.

  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 materials for bonding a substrate surface such as glass or cloth to an organic compound. 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 metal. Silane coupling agents are widely used as coating agents for various substrate surfaces using this property.

  As those utilizing these characteristics, a fluoroaminosilane compound represented by the following formula has been disclosed (see Patent Document 1).

（式中、Ｒ^１、Ｒ^２は炭素数１〜４のアルキル基、Ｑ^１はＣＨ_２ＣＨ_２ＣＨ_２又はＣＨ_２ＣＨ_２ＮＨＣＨ_２ＣＨ_２ＣＨ_２、ｈは１〜４の整数、ｉは２又は３である。）
しかしながら、この化合物は、パーフルオロポリエーテル基の部分が、ヘキサフルオロプロピレンオキサイド（ＨＦＰＯ）の２〜５量体と短いため、上記パーフルオロポリエーテル基の持つ特徴を十分に出すことができなかった

(Wherein R ¹ and R ² are alkyl groups having 1 to 4 carbon atoms, Q ¹ is CH ₂ CH ₂ CH ₂ or CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ , h is an integer of 1 to 4, and i is 2 or 3.)
However, since this compound has a short portion of perfluoropolyether group, which is as short as 2 to 5 mer of hexafluoropropylene oxide (HFPO), the characteristics of the perfluoropolyether group could not be sufficiently obtained.

  Conventionally, as an antireflection film for the purpose of improving contamination resistance, etc., on the surface of an antireflection layer comprising a single layer or a multilayer inorganic layer having a surface layer mainly composed of silicon dioxide formed by the PVD method, Those having a cured layer made of an organic polysiloxane polymer or a perfluoroalkyl group-containing polymer have been known (see Patent Document 2).

  However, when human contamination such as hand dirt or fingerprints adheres, it is difficult to wipe off with tissue paper etc., the contamination is spread on the thin film, and when rubbed strongly, the anti-reflection film is damaged, so satisfactory removal is achieved There was a problem that it was not possible.

  In general, a perfluoropolyether group-containing compound has the above-described characteristics, and an antireflection film using a perfluoropolyether-modified aminosilane represented by the following formula as an antifouling layer is obtained by taking advantage of these characteristics. It is disclosed (see Patent Documents 3 and 4). However, this antireflection film is excellent in water and oil repellency, antifouling properties, chemical resistance, lubricity, releasability, etc., but in the molecule of perfluoropolyether modified aminosilane used for the antifouling layer. It contains polar groups such as amide groups that have a high affinity for water, and since the ratio (wt%) of hydrolyzable groups in one molecule is small, it takes time to cure, Therefore, it has been desired to provide sufficient performance when used as a surface treatment agent.

（式中、Ｘ^３は加水分解性基、Ｒ^５は低級アルキル基、Ｒ^６は水素原子又は低級アルキル基、Ｑ^２はＣＨ_２ＣＨ_２ＣＨ_２又はＣＨ_２ＣＨ_２ＮＨＣＨ_２ＣＨ_２ＣＨ_２、ｅは６〜５０の整数、ｆは２又は３、ｃ及びｄはそれぞれ１〜３の整数。）

(Wherein X ³ is a hydrolyzable group, R ⁵ is a lower alkyl group, R ⁶ is a hydrogen atom or a lower alkyl group, Q ² is CH ₂ CH ₂ CH ₂ or CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ , e is an integer of 6 to 50, f is 2 or 3, and c and d are each an integer of 1 to 3.)

  In particular, antireflection films that are generally provided on the surface of visual devices and the like are likely to be contaminated with contaminants such as dirt, fingerprints, sweat, saliva, hairdressing, etc. Change, or the deposits appear white and the display content is unclear, so the contamination is more conspicuous than in the case of simple transparent plates. Providing an antireflection film that has excellent removability and maintains antifouling performance for a long time has been a long-standing problem.

  Therefore, a treatment agent having a hydrolyzable group at the end of the perfluoropolyether group-containing silane coupling agent is hardly contaminated, and is effective as a surface treatment agent that can easily wipe off the stain (see Patent Documents 5 and 6). In addition, the perfluoropolyether group-containing silane coupling agent represented by the following formula has two or three hydrolyzable groups at both ends, has excellent adhesion to the base material, is resistant to dirt, and is easy to wipe off the dirt. In addition, a perfluoropolyether-modified silane has been disclosed that has characteristics such as good surface slipperiness, resistance to scratches, and sustaining their performance (see Patent Document 7).

（式中、Ｒｆは二価の直鎖型パーフルオロポリエーテル基、Ｒは炭素数１〜４のアルキル基又はフェニル基、Ｘは加水分解性基、ｐは０〜２、ｑは１〜５の整数、ａは２又は３である。）

(In the formula, Rf is a divalent linear perfluoropolyether group, R is an alkyl group having 1 to 4 carbon atoms or phenyl group, X is a hydrolyzable group, p is 0 to 2, q is 1 to 5) , A is 2 or 3.)

  However, even if these surface treatment agents are used, dirt does not adhere, and it is necessary to wipe off the dirt frequently, and it is necessary to prevent scratches when wiping off dirt with tissue paper, etc. There is a problem with sustainability.

As for the ease of wiping off the dirt, if the surface is oil-repellent and the surface is slippery, it feels easy to wipe off. Although the conventional surface treatment agent has improved durability of water and oil repellency, the surface slipperiness is easily deteriorated by ultrasonic cleaning of water or an organic solvent.

In order to exhibit sufficient slipperiness, a film thickness of several molecular layers is necessary, but the conventional treatment agent has good adhesion between the base material and the first layer, but the first and second layers. In addition, the adhesion after that was insufficient. Therefore, development of a surface treatment agent with improved slipperiness persistence is awaited.

JP 58-167597 A Japanese Patent Laid-Open No. 62-148902 JP-A-11-29585 JP 2000-143991 A JP-A-9-157582 JP 2004-145283 A JP 2003-238777 A

  Accordingly, an object of the present invention is to provide a coating composition having a perfluoropolyether-polysiloxane copolymer-modified silane as a main component and capable of maintaining slipperiness.

  As a result of intensive studies in order to meet the above demand, the inventor used a composition comprising a mixture of two or more perfluoropolyether-polysiloxane copolymer-modified silanes represented by the following general formula (1). It has been found that the durability of the slipperiness to ultrasonic cleaning of water and fluorine-based solvents is greatly improved by treating a film or glass coated with an inorganic oxide such as silicon dioxide. It came.

  That is, the present invention provides the following average composition formula (1)

（式中、Ｒｆは２価のパーフルオロポリエーテル−ポリシロキサン共重合体含有基、Ｑはアミド、エーテル、エステル、アルキレン結合を含む基から選ばれる２価の連結基、Ｚは下記式（８）又は（９）で示されるポリシロキサンを含む２価の基、Ｒは炭素数１〜４のアルキル基またはフェニル基、Ｘは加水分解性基である。ａは２又は３、ｂは１〜１０の整数、ｙは１〜５の整数である。）で表されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランであって、Ｒｆが下記平均組成式（２）で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランとＲｆが下記平均組成式（３）で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランとの比率が１：９〜９：１で同時に含有することを特徴とする含フッ素コーティング剤組成物を提供する。

（式中、ｇは１〜２００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。）

（式中、ｙは１〜５の整数、ｈおよびｉは１〜２００の同じ又は異なっても良い整数である。Ｒ ^′ は上記と同じ。）
−（Ｚ−Ｑ）_p−Ｒｆ¹−（Ｑ−Ｚ）_p− （２）
−Ｒｆ¹−（Ｑ−Ｚ−Ｑ−Ｒｆ¹）_q− （３）
（式中、Ｒｆ¹は、２価のパーフルオロポリエーテル基、Ｚ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い。ｐは０又は１、ｑは１〜３の整数である。）

(In the formula, Rf is a divalent perfluoropolyether-polysiloxane copolymer-containing group, Q is a divalent linking group selected from amide, ether, ester, and a group containing an alkylene bond , and Z is the following formula (8 ) Or (9) is a divalent group containing a polysiloxane , R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, b is 1 to 10 is an integer of 10 and y is an integer of 1 to 5.) A perfluoropolyether-polysiloxane copolymer-modified silane represented by the following formula, wherein Rf is represented by the following average composition formula (2): The ratio of the ether-polysiloxane copolymer-modified silane and the perfluoropolyether-polysiloxane copolymer-modified silane represented by the following average composition formula (3) is 1: 9 to 9: 1 at the same time. The Providing a fluorine-containing coating composition according to symptoms.

(In the formula, g is an integer of 1 to 200. R ^' is the same or different alkyl group having 1 to 4 carbon atoms or phenyl group.)

(In the formula, y is an integer of 1 to 5, h and i are the same or different integers of 1 to 200, and R ^' is the same as above.)
_{- (Z-Q) p -Rf} 1 - (Q-Z) p - (2)
-Rf ^1- (QZQ-Rf ¹ ) _q- (3)
Wherein Rf ¹ is a divalent perfluoropolyether group, Z and Q are the same groups as described above, and may be the same or different. P is 0 or 1, and q is an integer of 1 to 3. .)

  The perfluoropolyether-polysiloxane copolymer-modified silane of the formula (1), which is the main component of the surface treatment agent of the present invention, has many hydrolyzable silyl groups at both ends of the molecule, and Rf is the above When both fluorine-containing organosilicon compounds represented by the average composition formulas (2) and (3) are contained at the same time, and mixed with a plurality of polyfunctional compounds and cured, both ends are firmly adhered to the substrate. In addition, since the treatment agents are in close contact with each other, the surface having water and oil repellency and low dynamic friction can be maintained for a long time.

  Hereinafter, the present invention will be described in more detail. The perfluoropolyether-polysiloxane copolymer-modified silane contained in the coating agent of the present invention has the following average composition formula (1):

（式中、Ｒｆは２価のパーフルオロポリエーテル−ポリシロキサン共重合体含有基、Ｑは２価の連結基、Ｚはシロキサン結合を有する少なくとも２価の基、Ｒは炭素数１〜４のアルキル基またはフェニル基、Ｘは加水分解性基である。ａは２又は３、ｂは１〜１０の整数、ｙは１〜５の整数である。）で表されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランであって、Ｒｆが下記平均組成式（２）で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランである。

(In the formula, Rf is a divalent perfluoropolyether-polysiloxane copolymer-containing group, Q is a divalent linking group, Z is at least a divalent group having a siloxane bond, and R is a carbon number of 1 to 4. An alkyl group or a phenyl group, X is a hydrolyzable group, a is 2 or 3, b is an integer of 1 to 10, and y is an integer of 1 to 5.) A siloxane copolymer-modified silane, wherein Rf is a perfluoropolyether-polysiloxane copolymer-modified silane represented by the following average composition formula (2).

In formula (1), Rf is a perfluoropolyether-polysiloxane copolymer-modified silane represented by the following average composition formula (2) and Rf is a perfluoropolyether-polysiloxane represented by the following average composition formula (3): Fluorine-containing, characterized in that it is simultaneously contained in a ratio of 1: 9 to 9: 1, preferably 2: 8 to 8: 2, more preferably 4: 6 to 6: 4 with the copolymer-modified silane It is a coating agent composition.
^{_{- (Z-Q) p -Rf}} 1 - (Q-Z) p - (2)
^{-Rf 1 - (Q-Z-} Q-Rf 1) q - (3)

(In the formula, Rf ¹ is a divalent perfluoropolyether group, Z and Q are the same groups as described above, and each may be the same or different. P is 0 or 1, and q is an integer of 1 to 3. .)

  Rf of the perfluoropolyether-polysiloxane copolymer modified silane represented by the above average composition formula (2) of the perfluoropolyether-polysiloxane copolymer modified silane represented by the above average composition formula (3) When the ratio exceeds 90%, the ratio of hydrolyzable groups in the vicinity of the polysiloxane group is less than 10% of the whole, so that the adhesion between the processing agents is deteriorated. On the other hand, when it is less than 10%, the ratio of hydrolyzable groups in the vicinity of the perfluoropolyether group is less than 10% of the whole, and therefore, the adhesion between the treatment agents is similarly bad, which is not preferable.

Here, Rf ¹ is a divalent perfluoropolyether-containing group, and it does not matter whether it is linear or branched. As the perfluoropolyether _structure, -C _{j F} 2j O- (wherein, h of each unit is an integer of 1 to 6 independently.) Those containing repeating units of, for example, the general formula _{(C j} F _2j O) _k and the like. 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 the case of perfluoropolyether groups, perfluoroether groups of various chain lengths are included. Among these, perfluoroethers having a repeating unit of a perfluoroether group having about 1 to 4 carbon atoms represented by the following units are shown. Polyether.
—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 (4), (5) and (6).

（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.)

  In the case of the above-mentioned perfluoropolyether-containing group, perfluoroether groups having various chain lengths are included, preferably a perfluoropolyether-containing group having a perfluoroether group having about 1 to 4 carbon atoms as a repeating unit. . The total number of repeating units in the chemical structural formula is preferably 1 to 60, more preferably 10 to 50. In addition, the molecular structure of perfluoropolyether is not limited to those exemplified.

Furthermore, in the formula (2), it is preferable in terms of the dynamic friction coefficient that Rf ¹ is a perfluoropolyether-containing group represented by the following general formula (7).
_{-CF 2 (OC 2 F 4)} e (OCF 2) f OCF 2 - (7)

(In the formula, e = 0 to 50, f = 1 to 50 and e + f = 2 to 60 are integers.)

Wherein, Q is a divalent group linking Rf group and Z group, Rf ¹ and Z, the Rf ¹ and Rf ^1, amides, ethers, esters, and the like groups containing an alkylene bond.

  Specific examples include the following.

In the above formula, Z may contain one or more selected from an oxygen atom, a nitrogen atom, a silicon atom and a sulfur atom, but is preferably a silicon functional group and at least a divalent group having a siloxane bond. It is preferable that Although it is better to have the Z group in terms of reactivity with the substrate, the Q group and the C _y H _2y group may be directly bonded.

  Specific examples include the following.

In the formulas (2) and (3), Z is preferably a divalent group containing polysiloxane, regardless of whether it is linear or branched. The polysiloxane structure is represented by the following formula (8) or (9), and examples thereof include polydimethylsiloxane. Here, R ^' is the same or different C1-C4 alkyl group or phenyl group.

ここで、ｇは１〜２００、好ましくは１〜１００、より好ましくは１０〜６０の整数である。

Here, g is an integer of 1 to 200, preferably 1 to 100, more preferably 10 to 60.

ここで、ｙは１〜５の整数、ｈおよびｉは１〜２００、好ましくは１〜１００、より好ましくは１０〜６０の同じ又は異なっても良い整数である。

Here, y is an integer of 1 to 5, and h and i are 1 to 200, preferably 1 to 100, more preferably 10 to 60, which may be the same or different integers.

  Specific examples 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 the formula, 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. Although b is 1-10 and 1-5 are preferable from the coexistence of the adhesiveness to a base material, and antifouling performance, it is not limited to this.

  The perfluoropolyether-polysiloxane copolymer-modified silane forms a cured film on the substrate, but forms a microphase separation structure. In the case of a perfluoropolyether-polysiloxane copolymer-modified silane alone, there is a functional group only in either the perfluoroether phase or the polysiloxane phase, and it is difficult to fix both phases with chemical bonds. . Therefore, although the base material adheres firmly to the treatment agent, the adhesion between the treatment agents is weak, so even if several molecular layers can be formed, they are easily washed away by ultrasonic cleaning.

Therefore, in the present invention, by mixing two kinds of perfluoropolyether-polysiloxane copolymer-modified silane, it is possible to fix the perfluoroether phase and the polysiloxane phase with chemical bonds.

  The present invention provides a raw material and a surface treatment agent for forming a cured film using two or more of the above-mentioned perfluoropolyether-polysiloxane copolymer-modified silanes or partially hydrolyzed condensates thereof.

  The two or more perfluoropolyether-polysiloxane copolymer-modified silanes must contain at least both of the fluorine-containing organosilicon compounds represented by (2) and (3), and (2) The mixing ratio of (3) is preferably from 1: 9 to 9: 1, more preferably from 2: 8 to 8: 2 in terms of molar ratio.

  The molecular weights of the perfluoropolyether-polysiloxane copolymer-modified silane to be mixed are preferably equal.

  The perfluoropolyether-polysiloxane copolymer-modified silane forms a cured film on the substrate, but forms a microphase separation structure. In the case of a perfluoropolyether-polysiloxane copolymer-modified silane carrier, there is a functional group only in either the perfluoroether phase or the polysiloxane phase, and it is difficult to fix either phase with a chemical bond. It is. However, as in the present invention, by mixing two kinds of perfluoropolyether-polysiloxane copolymer-modified silanes, the perfluoroether phase and the polysiloxane phase can be fixed by chemical bonds.

  It is preferable to add a conventionally known curing catalyst to the coating agent 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, and perfluoroalcohols.

  The perfluoropolyether-polysiloxane composition using the perfluoropolyether-polysiloxane copolymer-modified silane of the present invention can be used for various applications. Since it has a low surface energy, it is excellent in releasability and water repellency, and can be used as a moisture-proof seal part, a fuel cell sealant, and a surface treatment agent. For example, it can be applied to the following. Sanitary products such as bathtubs, washstands, electric razors, makeup tools, kitchen building materials, window glass for automobiles, trains, aircraft, etc., headlamp covers, liquid crystal displays, plasma displays, organic EL display car navigation systems, mobile phones, anti-reflection Optical members such as filters and polarizing plates, spectacle lenses, telephone box water repellency, paint and anti-graffiti paints, water repellent agents for fine arts, compact discs, DVDs, other paint additives, resin modifiers, inorganics It can be applied to improve the fluidity and dispersibility of fillers and improve the lubricity of tapes and films.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by this. In the following examples, the physical properties in the table are measured by the following test methods.

[Examples 1-7]
Compounds 1 to 5 are dissolved in HFE-7200 (manufactured by Sumitomo 3M), 0.2 wt% solution is prepared, and each is mixed at a specified ratio, and 0.8 wt% perfluorocarboxylic acid with respect to the active ingredient Was added to obtain a treating agent. The slide glass was immersed in the treatment agent for 30 seconds, then pulled up at a speed of 150 mm / min, and left in an atmosphere of 25 ° C. and humidity of 40% for 24 hours to form a cured film. Table 1 summarizes the mixing ratio of each treatment agent.

[Evaluation of feel]
For the touch, a blind test was performed when the surface of the slide glass was rubbed with Bencot (Asahi Kasei Co., Ltd.). The evaluation criteria are as follows. Samples used at the initial stage and after 2000 reciprocations (ben cotton, 0.5 kg load) were used.
A: The touch is particularly excellent.
○: Feel good.
Δ: Normal.
X: The touch is bad.
[Evaluation of dynamic friction coefficient]
The dynamic friction coefficient for Bencott (Asahi Kasei Co., Ltd.) was measured using a surface property tester manufactured by Shinto Kagaku.
[Evaluation of film adhesion]
The dynamic friction coefficient and feel before and after ultrasonic cleaning with a fluorine-based solvent AK225 (Asahi Glass Co., Ltd.) were evaluated.

[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

[Compound 5]

[Compound 6]

（ｐ／ｑ＝０．９ Ｍｗ≒４０００〜６０００）

(P / q = 0.9 Mw≈4000-6000)

  The evaluation results are shown in Table 1.

Examples 1 to 8 and Comparative Examples 1 to 4 each contain a perfluoropolyether (PFE) group and a polysiloxane group, and compared with the case where a treatment agent containing only a PFE group was used (Compound 5). The touch was excellent. Moreover, when the siloxane unit became long, it was more excellent in touch.
After ultrasonic cleaning with a fluorinated solvent, in Examples, the coefficient of dynamic friction was low and the touch was excellent. By mixing two kinds of perfluoropolyether-polysiloxane copolymer-modified silane, there is a hydrolyzable group in the vicinity of PFE group and polysiloxane. This is considered to be because the film thickness can be fixed and a film thickness sufficient to achieve a low dynamic friction coefficient can be maintained.
In addition, Examples 1 to 6 in which the molecular weights of the compounds to be mixed were about the same, the durability of the dynamic friction coefficient was good as compared with Examples 7 and 8 having greatly different molecular weights.
On the other hand, in the comparative example, although the water contact angle did not decrease, the dynamic friction coefficient increased and the feel became worse. Since the adhesiveness between the treatment agents is poor, it is considered that the treatment agent was easily washed away by ultrasonic cleaning with a fluorine-based solvent, and only a monomolecular layer remained, and a sufficient film thickness could not be maintained.
In view of the above, the coating agent composition using the perfluoropolyether-polysiloxane copolymer-modified silane shown in the present invention forms a strong film on the surface of the base material and is excellent in adhesion between the processing agents. It is water and oil repellent and can maintain a low dynamic friction surface.

Claims (5)

The following average composition formula (1)

(In the formula, Rf is a divalent perfluoropolyether-polysiloxane copolymer-containing group, Q is a divalent linking group selected from amide, ether, ester, and a group containing an alkylene bond , and Z is the following formula (8 ) Or (9) is a divalent group containing a polysiloxane , R is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a hydrolyzable group, a is 2 or 3, b is 1 to 10 is an integer of 10 and y is an integer of 1 to 5.) A perfluoropolyether-polysiloxane copolymer-modified silane represented by the following formula, wherein Rf is represented by the following average composition formula (2): The ratio of the ether-polysiloxane copolymer-modified silane and the perfluoropolyether-polysiloxane copolymer-modified silane represented by the following average composition formula (3) is 1: 9 to 9: 1 at the same time. The The fluorine-containing coating composition according to symptoms.

(In the formula, g is an integer of 1 to 200. R ^' is the same or different alkyl group having 1 to 4 carbon atoms or phenyl group.)

(In the formula, y is an integer of 1 to 5, h and i are the same or different integers of 1 to 200, and R ^' is the same as above.)
_{- (Z-Q) p -Rf} 1 - (Q-Z) p - (2)
-Rf ^1- (QZQ-Rf ¹ ) _q- (3)
Wherein Rf ¹ is a divalent perfluoropolyether group, Z and Q are the same groups as described above, and may be the same or different. P is 0 or 1, and q is an integer of 1 to 3. .) The formula (2) or (3), wherein Rf ¹ is selected from groups containing perfluoropolyether groups represented by the following general formulas (4), (5), and (6): The fluorine-containing coating agent composition as described.

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, and m + n is 2 to 200, s. Is an integer of 0 to 6. The arrangement of repeating units in the general formula is random.)

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

Wherein Y is an 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 is 2 to 200. The arrangement of repeating units in the general formula is Random.) 2. The fluorine-containing coating according to claim 1, wherein in formulas (2) and (3), Rf ¹ is a group containing a perfluoropolyether group selected from the group represented by the following general formula (7): Agent composition.
_{-CF 2 (OC 2 F 4)} e (OCF 2) f OCF 2 - (7)
(In the formula, e = 0 to 50, f = 1 to 50 and e + f = 2 to 60 are integers.)   The fluorine-containing coating agent composition according to any one of claims 1 to 3, wherein Q is selected from the group represented by the following formula.

  5. A carboxylic acid having a molecular weight of 100 or more and a fluorine content in the molecule of 25 wt% or more, or a derivative thereof, which can generate a carboxylic acid during use. The fluorine-containing coating agent composition of any one of these.