JPH09202648A - Surface treatment method - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide a surface treatment method for a base material, which has a sufficient anti-staining action, has a long-lasting action, and also has sufficient weather resistance. SOLUTION: The silicon-containing organic fluorine-containing polymer (1) represented by the following general formula (I), the fluorine-containing organic solvent (2), and the silane compound (however, the silicon-containing organic fluorine-containing polymer (1) is excluded. ] A surface treatment method in which a treatment liquid containing (3) is applied to the surface of a substrate. Embedded image In the formula, Rf represents a perfluoroalkyl group. Z is
Represents a fluorine or trifluoromethyl group. a, b, c,
d and e each independently represent an integer of 0 or 1 or more, and a + b + c + d + e is at least 1 or more,
The order in which the repeating units a, b, c, d, and e are present is not limited in the formula. Y represents hydrogen or an alkyl group having 1 to 4 carbon atoms. X represents hydrogen, bromine or iodine. R ¹ represents a hydroxyl group or a hydrolyzable substituent. R ² represents hydrogen or a monovalent hydrocarbon group.
l represents 0, 1 or 2. m represents 1, 2 or 3. n represents an integer of 1 or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface treatment method for a base material, which gives a sufficient anti-staining effect to the surface of the base material and also excellent weather resistance.

[0002]

2. Description of the Related Art Substrates such as glass and resin are used for automobile parts,
It is widely used as OA equipment, home electric appliances, etc. On the surface of these base materials, dust floating in a car, an office, a room, etc. adheres, or an oily substance that is difficult to wipe off is mixed with food, oil for equipment, etc. Since fingerprints are attached by hands and contaminated, it is difficult for these contaminants to adhere, and further, it is necessary to devise an antifouling device that can easily remove the contaminants once attached. Become.

As a means for antifouling treatment of the glass surface, Japanese Unexamined Patent Publication (Kokai) No. 1-126244 discloses a coating film obtained by directly coating a polymer substance such as polydimethylsiloxane on the glass surface or dipping it in a treatment agent. Techniques for forming are disclosed. Further, a technique of forming a chemisorption monomolecular film containing fluorine on the glass surface by a chemisorption method is also known.

In Japanese Patent Publication No. 7-53913, as a means for antifouling treatment of a metal surface, a chromate skin containing a silica sol silane coupling agent is formed on an upper layer of a zinc plating skin, and an isocyanate system is formed on the upper layer. A technique relating to an organic composite plated steel sheet coated with a thin film using a coating composition is disclosed.

Further, for the purpose of enhancing the antifouling effect of the antireflection filter, there has been proposed a technique of forming a film of a compound obtained by silanizing a perfluoropolyether compound on the antireflection film.

[0006]

However, all of the above-mentioned techniques have certain effects in order to enhance the anti-contamination action, but their effects are notable under severe conditions such as outdoor exposure. It was reduced and was not satisfactory in terms of weather resistance. In view of the above situation,
It is an object of the present invention to provide a surface treatment method for a base material which has a sufficient anti-staining action, the action is permanent, and also has sufficient weather resistance.

[0007]

The surface treatment method of the present invention comprises a silicon-containing organic fluorine-containing polymer (1) represented by the following general formula (I), a fluorine-containing organic solvent (2), and a silane compound ( A method for treating a surface of a substrate, which comprises applying a treatment liquid containing 3) to the surface of the substrate.

[0008]

Embedded image

In the formula, Rf represents a perfluoroalkyl group. Z represents a fluorine or trifluoromethyl group.
a, b, c, d, and e each independently represent 0 or an integer of 1 or more, and a + b + c + d + e is at least 1
As described above, the order in which the repeating units defined by a, b, c, d, and e are present is not limited in the formula. Y
Represents hydrogen or an alkyl group having 1 to 4 carbon atoms. X is
Represents hydrogen, bromine or iodine. R ¹ represents a hydroxyl group or a hydrolyzable substituent. R ² represents hydrogen or a monovalent hydrocarbon group. l represents 0, 1 or 2. m is 1,
Represents 2 or 3. n represents an integer of 1 or more. Hereinafter, the present invention will be described in detail.

The surface treatment method of the present invention comprises applying a treatment liquid to the surface of a substrate. The first component of the treatment liquid is the silicon-containing organic fluoropolymer (1) represented by the general formula (I). In the formula represented by the above general formula (I), Rf is not particularly limited as long as it is a perfluoroalkyl group that constitutes an organic fluoropolymer, and is, for example, a straight chain having 1 to 16 carbon atoms or Examples include branched ones. Preferably, CF ₃ −, C ₂ F
₅ − and C ₃ F ₇ −.

Z in the above general formula (I) may be fluorine or a trifluoromethyl group. The above general formula (I)
A, b, c, d, and e represent the number of repeating units of the perfluoropolyether chain constituting the main skeleton of the silicon-containing organic fluorine-containing polymer, and are 0 or an integer of 1 or more.
Although it is not particularly limited as long as + b + c + d + e is 1 or more, it is preferably independently 0 to 200, and more preferably independently 0 to 50 in consideration of the molecular weight of the silicon-containing organic fluorine-containing polymer described later. It is. a + b + c + d + e is preferably 1 to 100.

The order of existence of the repeating units surrounded by a, b, c, d, and e is described in this order in the general formula (I) for convenience, but the usual perfluoropolyether chain structure is used. In view of this, the bonding order of each of these repeating units is not limited to this order.

Y in the above general formula (I) represents hydrogen or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms is not particularly limited, and includes, for example, methyl, ethyl, propyl, butyl and the like, and may be linear or branched. X of the above general formula (I)
Represents hydrogen, bromine or iodine. When X is bromine or iodine, the silicon-containing organic fluorine-containing polymer of the present invention has high radical reactivity, and therefore it is convenient to bond with another compound by a chemical bond.

In the above general formula (I), 1 represents the carbon number of the alkylene group existing between the carbon constituting the perfluoropolyether chain and the silicon bonded to it, and 0, 1
Or 2, but more preferably 0.

M in the general formula (I) represents the number of bonds of the substituent R ¹ bonded to silicon, and is 1, 2 or 3.
R ² is bonded to the silicon where the substituent R ¹ is not bonded.

R ¹ represents a hydroxyl group or a hydrolyzable substituent. The hydrolyzable substituent is not particularly limited, and is preferably, for example, halogen,
-OR ³ , -OCOR ³ , -OC (R ³ ) = C (R ⁴ )
^{_{2, -ON = C (R 3}} ) 2, -ON = CR 5 [ wherein, R
³ represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group,
R ⁴ represents hydrogen or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ⁵ represents a divalent aliphatic hydrocarbon group having 3 to 6 carbon atoms. ] Etc. can be mentioned. More preferably, chlorine, -OCH _3, is -OC ₂ H _5.

R ² represents hydrogen or a monovalent hydrocarbon group. The monovalent hydrocarbon group is not particularly limited,
Preferred examples include methyl, ethyl, propyl, butyl and the like, which may be linear or branched.

In the general formula (I), n represents an integer of 1 or more, and there is no particular upper limit, but it is preferably an integer of 1 to 10 in order to achieve the object of the present invention. The above n
Represents an integer in the general formula (I), and the silicon-containing organic fluoropolymer according to the present invention exists as a mixture of the polymer represented by the general formula (I) having such an integer n. Is also good. As described above, when the silicon-containing organic fluoropolymer is present as a mixture, the above n can be represented as an average value in the mixture, and when the silicon-containing organic fluoropolymer is present as a mixture, In consideration of the object of the present invention, the average value of n is preferably 1.3 to 3, and particularly preferably 1.5 to 2.5.

The molecular weight of the silicon-containing organic fluorine-containing polymer is preferably 5 × 10 ² to 1 × 10 ⁵ . 5 x 10
^If it is less than ² , the effect of the present invention will not be exhibited, and if it exceeds 1 × 10 ⁵ , processability will be poor. More preferably, 1 × 10
^{It is 3} to 1 × 10 ⁴ .

Preferred examples of the above silicon-containing organic fluorine-containing polymer include those represented by the following general formula (II).

[0021]

Embedded image

In the formula, p represents an integer of 1 or more. Y,
X, R ¹ , R ² , l, m, and n are the same as described above. P in the general formula (II) is not particularly limited as long as it is an integer of 1 or more, but is preferably 1 to 200, and more preferably 1 in consideration of the molecular weight of the silicon-containing organic fluoropolymer of the present invention. ~ 50.

The molecular weight of the silicon-containing organic fluorine-containing polymer is preferably 5 × 10 ² to 1 × 10 ⁵ . 5 x 10
^If it is less than ² , the effect of the present invention will not be exhibited, and if it exceeds 1 × 10 ⁵ , processability will be poor. More preferably, 1 × 10
^{It is 3} to 1 × 10 ⁴ .

The above silicon-containing organic fluorine-containing polymer is
Usually, commercially available perfluoropolyether is used as a raw material and, for example, iodine is introduced into the terminal, and then, for example, the following general formula [wherein, Y, R ¹ , R ² , l,
m is the same as above. For example, by reacting a vinylsilane compound represented by the formula

[0025]

[Chemical 6]

The second component constituting the above treatment liquid used in the surface treatment method of the present invention is the fluorine-containing organic solvent (2). The fluorine-containing organic solvent (2) is not particularly limited, and examples thereof include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane and HCFC225. Among them, HCFC225 is preferable because it can easily dissolve the silicon-containing organic fluoropolymer (1) and is easily available.

The third component constituting the above treatment liquid used in the surface treatment method of the present invention is a silane compound (3). The silane compound (3) is not particularly limited,
For example, general formula (III) Si (OR ¹¹ ) ₄ (III) [In the formula, R ¹¹ represents an aliphatic hydrocarbon group, and the carbon number thereof is not particularly limited. Alkoxide compounds of silicon represented by the general formula (III), and partial hydrolysis condensation products of the compounds represented by the general formula (III). Above all,
Tetraethoxysilane is preferred because it is easily available.

The constituent ratios of the respective components (1), (2) and (3) constituting the above-mentioned treatment liquid used in the surface treatment method of the present invention are not particularly limited, but (1) :( 2) is It is preferable that the weight ratio is 1: 1 to 1: 10000. (1)
If the amount of the component is too large, the viscosity of the liquid increases, which impairs workability, and if it is too small, the effect of preventing contamination becomes insufficient. More preferably, it is 1: 4 to 1: 1000. The weight ratio of (1) :( 3) is preferably 10: 1 to 1: 100. If the amount of component (1) is too large, the effect of improving the weather resistance will be insufficient, and if it is too small, the effect of preventing contamination will be insufficient. More preferably 5:
1 to 1:10.

In applying the treatment liquid of the present invention, for example, fine powder fillers such as silica, alumina, titanium oxide, carbon and cement, alkoxides such as titanium and aluminum, and other low molecular weight polytetrafluoroethylene, A fine powder of a fluororesin such as a tetrafluoroethylene / hexafluoropropylene copolymer can be added as a hardness adjusting agent or a bulking agent. Further, the hardness can be adjusted by further adding a usual crosslinking agent or a curing catalyst such as water, hydrochloric acid, sulfuric acid, carboxylic acid, sulfonic acid and the like.

In applying the treatment liquid of the present invention, a method of applying the treatment liquid on the surface of a target substrate can be adopted. Examples of the coating method include brush coating, spray coating, spin coating, dip coating,
Roll coating, gravure coating, curtain flow coating and the like can be mentioned.

In the surface treatment method of the present invention, the thickness of the layer formed by the treatment liquid is not particularly limited, but is preferably 0.001 to 0.03 μm. 0.
If it is less than 001 μm, the antifouling effect becomes poor,
When it exceeds 0.03 μm, the layer is too thick and the use is impaired, which is not preferable.

The second surface treatment method of the present invention is a treatment liquid containing a silicon-containing organic fluoropolymer (1) represented by the general formula (1) and a fluorine-containing organic solvent (2). M) is applied to the surface of a base material having an underlayer formed on the surface using a treatment liquid (N) containing a silane compound [excluding the silicon-containing organic fluorine-containing polymer (1)] (3). It consists of doing.

The silane compound (3) is treated with an organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl acetate or acetone or a water solvent to give a treatment liquid (N) having a predetermined concentration. This concentration is not particularly limited, but it is preferably in the range of 2 to 80% by weight. If it is less than 2% by weight, it takes a long time to form the silica sol, and if it exceeds 80% by weight, the liquid viscosity becomes too high and the workability is impaired. Treatment liquid (N)
After adding an ordinary catalyst, for example, hydrochloric acid, to the silica sol by allowing it to stand for a predetermined time, it is diluted with the above solvent to a concentration suitable for the coating operation. The standing time is not particularly limited, but is, for example, 2 to 10 days. The dilution concentration varies depending on the desired thickness of the underlayer, but is, for example, in the range of 0.2 to 2% by weight.

Next, the diluted treatment liquid (N) is applied to the surface of the base material. As the coating method, for example, brush coating, spray coating, spin coating, dip coating, roll coating,
Examples include gravure coat painting and curtain flow painting. By the above operation, a gel layer of silanol polymer is formed on the surface of the base material.

Next, by heating the above-mentioned base material, a base layer containing silicon oxide as a main component can be formed. The heating temperature varies depending on the substrate, but for example, 100
~ 300 ° C. The heating time is not particularly limited, but is, for example, in the range of 10 minutes to 3 hours. The thickness of the underlying layer formed is not particularly limited, but is usually 0.05.
Is in the range of 0.1 μm.

Thereafter, the treatment liquid (M) is applied to the surface of the base material having the underlayer formed on the surface. Examples of the coating method include brush coating, spray coating, spin coating, dip coating, roll coating, gravure coating, curtain flow coating, and the like.

In the surface treatment method of the present invention, the thickness of the layer formed by the treatment liquid (M) is not particularly limited, but is preferably 0.001 to 0.03 μm. If it is less than 0.001 μm, the anti-contamination action becomes poor, and if it exceeds 0.03 μm, the layer is too thick to cause trouble in use, which is not preferable.

The substrate to which the surface treatment method of the present invention can be applied includes, for example, the easily polluted portions such as those listed below. Tie pins, necklaces, earrings and other ornaments; water faucets, brass instruments, woodwind instruments, golf clubs, door handles, dumbbells,
Metal or plated products such as blades; ceramic materials such as insulators, tiles, sanitary ware, tableware, roof tiles; stone materials such as gravestones, go stones, marble; paper products such as wallpaper, bran paper, books, posters, photographs; wallets, Leather products such as shoes, bags, watch bands, and baseball gloves.

Home appliances such as fan blades, microwave oven doors, refrigerator surfaces, etc .; contact glass for copy machines, OH
P body mirror, OHP sheet, keyboard, telephone,
Office-related items such as office desks; household items such as glasses, cupboard doors, mirrors, window glasses, light umbrellas, chandeliers; building materials such as show windows, telephone boxes, and aquarium glasses;
Vehicle glass, vehicle parts such as painted surface of vehicle body; glasses frame, underwater glasses glass, goggles, helmet, cover glass for watch dial, pachinko machine glass, playing cards, mahjong pie, etc .; furniture, Painted surface such as piano.

The surface treatment method of the present invention is characterized in that the anti-contamination action is permanent and that it has sufficient weather resistance. Therefore, it is suitable for applying the surface treatment method of the present invention. Among the above various base materials, for example, the following are preferable. Door handles; ceramic materials such as roof tiles; stone materials such as tombstones, go stones, marbles; contact glass for copy machines; window glass; vehicle parts such as vehicle glass and painted surfaces of car bodies; pachinko glass, playing cards, mahjong pie Playground equipment such as.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Synthesis Example 1 2617 g (10.3 mol) iodine, 213.2 g (1.54 mol) potassium carbonate in a 2.0 L four-necked flask equipped with a stirrer, dropping funnel, reflux condenser and thermometer. , And 9000 g of hexachloro-1,3-butadiene were charged, and the chemical formula F- (CF ₂ CF ₂ CF ₂ O) n was added under a nitrogen stream while maintaining the system temperature at 160 ° C.
Ω-fluoropolyperfluorooxetane acylfluoride represented by —CF ₂ CF ₂ COF (average molecular weight 3
900) 4000 g (1.03 mol) was added dropwise at a rate of 10 mL / min.

After completion of dropping, the reaction temperature was raised to 185 ° C. and the reaction was carried out for 20 hours. After completion of the reaction, the system was cooled, potassium salts were filtered off, and the lower layer was separated from the liquid phase separated into two layers using a separating funnel. This was washed several times with acetone, then dissolved in 1 L of perfluorohexane, and fine insoluble matter was filtered off with a glass filter. By completely distilling off volatile components from the obtained solution under reduced pressure, 3890 g (yield 95%) of the formula F- (C
_{F 2 CF 2 CF 2 O)} ω represented by n -CF ₂ CF ₂ I
-Fluoropolyperfluorooxetane iodide was obtained. From infrared absorption spectrum, -C at 1890 cm ^-1
(= O) absorption of F had completely disappeared, resulting newly absorbed -CF ₂ I to 910 cm ^-1. From ¹⁹ F-NMR using trichlorofluoromethane (CFC-11) as a standard, 2
The absorption of 0.7 ppm of -C (= O) F disappeared completely,
New to -66.7Ppm, cause absorption derived from -OCF ₂ C F ₂ I, in -87.6ppm, -OC F ₂ CF
Absorption due to ₂ I occurred. From the integrated value, the conversion rate is 1
It was calculated to be 00%.

Synthesis Example 2 2 equipped with a stirrer, dropping funnel, reflux condenser and thermometer
00mL4 one during neck flask was synthesized in Synthesis Example 1 formula _{F- (CF 2 CF 2 CF 2} O) represented by n -CF ₂ CF ₂ I ω- fluoropolyether perfluoro oxetane iodide 40g die chlorofluorocarbon solvent What was dissolved in 80 g of S-316 (manufactured by Daikin Industries, Ltd.) and 1.5 g of di-t-butyl peroxide (1 × 10 ^-2 mol) were charged, and the system was sufficiently replaced with nitrogen, and then under a nitrogen stream. From the dropping funnel, 16.1 g (0.10 g) of vinyltrichlorosilane
Mol) was added dropwise. After completion of dropping, the temperature in the system was raised to 120 ° C. and the reaction was carried out for 4 hours. After completion of the reaction, the volatile matter was completely distilled off under reduced pressure to obtain 38.7 g (yield 90%) of a silicon-containing organic fluoropolymer (A) having iodine at the terminal. ¹⁹ F-NM with CFC-11 as standard
From R, the absorption at -66.7 ppm and -87.6 ppm disappeared completely, and a wide absorption band appeared at -89.2 to -90.0 ppm. Moreover, from ¹ H-NMR, 1.4-
Although broad absorption band appeared at 3.0 ppm, the chemical formula as an internal standard _{F- (CF 2 CF 2 CF 2} O) n -CF 2 CF
_The degree of polymerization of trichlorovinylsilane was calculated by adding 5.0 mol% of ω-fluoropolyperfluorooxetane hydride represented by ₂ H, and it was 2.0.

Synthesis Example 3 2 equipped with a stirrer, dropping funnel, reflux condenser and thermometer
34.4 g (8 × 1) of the silicon-containing organic fluoropolymer (A) synthesized in Synthesis Example 2 in a 00 mL four-necked flask.
0 ^-3 mol) were charged which was dissolved in perfluorohexane 50 g, it was strong by stirring dispersing zinc 2.1g (3.2 × 10 ^-2 mol). The system was cooled in an ice water bath, and 10 g of anhydrous methanol was added dropwise under a nitrogen stream. After completion of dropping, the ice-water bath was removed, and the mixture was reacted under heating under reflux for 2 hours. After completion of the reaction, insoluble matter was filtered off, and the lower layer was separated from the liquid phase separated into two layers using a separating funnel. The obtained solution was washed three times with anhydrous methanol, and the volatile matter was completely distilled off under reduced pressure to give 31.6 g of a silicon-containing organic fluoropolymer (B) having a hydrogenated end (yield: 92%).
^{From 1} H-NMR, absorption of Si—OCH ₃ appeared at 3.5 ppm. As an internal standard, the chemical formula F- (CF ₂ CF ₂
5.0 mol% of ω-fluoropolyperfluorooxetane hydride represented by CF ₂ O) n-CF ₂ CF ₂ H is added, and the integrated intensity of a wide absorption band of 1.2 to 3.0 ppm is 16. It was confirmed that the degree of polymerization was 2.0 from the fact that it increased by 0% and the intensity ratio with the absorption band of 3.5 ppm.

Example 1 Silicon-containing organic fluorine-containing polymer (B) obtained in Synthesis Example 3
0.1 wt% was mixed with 99.8 wt% of HCFC225 and 0.1 wt% of tetraethoxysilane to prepare a treatment liquid. The glass plate was washed with water before use and then thoroughly washed with methanol and acetone. The glass plate thus prepared was dipped in the above treatment solution for 1 minute and pulled up, and then 60 ° C. under the condition of 80% RH.
Let stand for minutes. Then, it was thoroughly washed with HCFC225 to remove excess molecules of the treatment liquid. The sample prepared in this manner was placed in a sunshine weatherometer (SUV-W13, manufactured by Iwasaki Electric Co., Ltd.) for 16 hours (equivalent to 3.3 years).
Was subjected to the accelerated weathering resistance test, and the contact angles with water before and after the test were compared. The contact angle with water was measured using a contact angle meter (CA-DT type manufactured by Kyowa Interface Science Machine Co., Ltd.). The results are shown in Table 1.

Comparative Example 1 Silicon-containing organic fluorine-containing polymer (B) obtained in Synthesis Example 3
A treatment liquid was prepared in the same manner as in Example 1 except that 0.19 wt% of HCFC225 was mixed with 99.9 wt% to prepare a treatment liquid, and the test liquid was subjected to the same test. Table 1 shows the results
It was shown to.

[0048]

[Table 1]

[0049]

Since the surface treatment method of the present invention has the above-mentioned constitution, it has a sufficient anti-contamination action, the action is permanent, and also has sufficient weather resistance, especially in the severe conditions such as outdoor exposure. It can be suitably used for a base material that requires a pollution prevention action under various conditions.

Claims (5)

[Claims] 1. A silicon-containing organic fluorine-containing polymer (1) represented by the following general formula (I), a fluorine-containing organic solvent (2), and a silane compound (provided that the silicon-containing organic fluorine-containing polymer (1) is Excluding] A method for treating a surface of a substrate, which comprises applying a treatment liquid containing (3) to the surface of the substrate. Embedded image In the formula, Rf represents a perfluoroalkyl group. Z is
Represents a fluorine or trifluoromethyl group. a, b, c,
d and e each independently represent an integer of 0 or 1 or more, and a + b + c + d + e is at least 1 or more,
The order in which the repeating units a, b, c, d, and e are present is not limited in the formula. Y represents hydrogen or an alkyl group having 1 to 4 carbon atoms. X represents hydrogen, bromine or iodine. R ¹ represents a hydroxyl group or a hydrolyzable substituent. R ² represents hydrogen or a monovalent hydrocarbon group.
l represents 0, 1 or 2. m represents 1, 2 or 3. n represents an integer of 1 or more. 2. A treatment liquid (N) containing a silane compound [excluding the silicon-containing organic fluorine-containing polymer (1) represented by the following general formula (1)] (3) on the surface of the substrate. After coating to form a base layer, a treatment liquid (M) containing a silicon-containing organic fluorine-containing polymer (1) represented by the following general formula (1) and a fluorine-containing organic solvent (2). Is applied on the base layer. Embedded image In the formula, Rf represents a perfluoroalkyl group. Z is
Represents a fluorine or trifluoromethyl group. a, b, c,
d and e each independently represent an integer of 0 or 1 or more, and a + b + c + d + e is at least 1 or more,
The order in which the repeating units a, b, c, d, and e are present is not limited in the formula. Y represents hydrogen or an alkyl group having 1 to 4 carbon atoms. X represents hydrogen, bromine or iodine. R ¹ represents a hydroxyl group or a hydrolyzable substituent. R ² represents hydrogen or a monovalent hydrocarbon group.
l represents 0, 1 or 2. m represents 1, 2 or 3. n represents an integer of 1 or more. 3. The silicon-containing organic fluorine-containing polymer has a molecular weight of 5 × 10 ² to 1 × 10 ^5.
Or the surface treatment method described in 2. 4. A silicon-containing organic fluorine-containing polymer (1)
Is a silicon-containing organic fluorine-containing polymer represented by the following general formula (II), The surface treatment method according to claim 1 or 2. Embedded image In the formula, p represents an integer of 1 or more. Y represents hydrogen or an alkyl group having 1 to 4 carbon atoms. X represents hydrogen, bromine or iodine. R ¹ represents a hydroxyl group or a hydrolyzable substituent. R ² represents hydrogen or a monovalent hydrocarbon group. l
Represents 0, 1 or 2. m represents 1, 2 or 3.
n represents an integer of 1 or more. 5. The silicon-containing organic fluorine-containing polymer has a molecular weight of 5 × 10 ² to 1 × 10 ^5.
The surface treatment method described.