JP2010047680A - Reactive fluorine-containing oligomer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new reactive fluorine-containing oligomer having highly branched perfluoroalkenyl group on the main chain thereof. <P>SOLUTION: This reactive fluorine-containing oligomer has a polyacrylate main chain structure, where the structure has acrylate units having ester groups linked with specified side chains [-R<SP>1</SP>-O-Rf], [-R<SP>2</SP>-OH], [-R<SP>2</SP>-O-CO-NH-(O-CO-CR<SP>4</SP>=CH<SB>2</SB>)<SB>x</SB>] and [-R<SP>5</SP>] of n, m, p and q pieces, respectively, where in above formulas, R<SP>1</SP>, R<SP>2</SP>, R<SP>3</SP>and R<SP>5</SP>are 1-50C, 1-100C, 2-10C and 1-50C saturated aliphatic hydrocarbon groups, respectively, where R<SP>1</SP>and R<SP>2</SP>are bivalent, R<SP>3</SP>is bivalent or trivalent and R<SP>5</SP>is monovalent; R<SP>4</SP>, R<SP>6</SP>to R<SP>8</SP>are each hydrogen or a methyl group; n and m are each an integer of 1-30; p+q is an integer of 1-60; x is 1 or 2; and Rf is a specified perfluoroalkenyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a reactive fluorine-containing oligomer useful as a surface treatment agent, a surface modifier, and the like for resins, films, fibers, glass, metals and the like, and a method for producing the same.

  In general, as a useful method for imparting various properties such as water / oil repellency and antifouling properties to the surface of resin, film, fiber, glass, metal, etc., a compound having a fluorocarbon chain introduced into the molecule is applied to the surface. Such a method is widely used.

Fluorine-containing oligomers are known to be useful as surfactants, surface modifiers, antistatic agents, and dispersants (Patent Document 1). However, since fluorine-containing oligomers have a weak binding force to the surface of resins, etc., they temporarily exhibit various properties such as water and oil repellency and antifouling properties, but they must be continuously improved in surface properties. In addition, there was a problem that the surface strength of the resin or the like was lowered. In addition, no fluorine-containing oligomer having a highly branched perfluoroalkyl group or perfluoroalkenyl group in the main chain has been reported.
JP 2006-249130 A

  The main object of the present invention is to provide a novel reactive fluorine-containing oligomer having a highly branched perfluoroalkenyl group in the main chain.

That is, this invention provides the reactive fluorine-containing oligomer of the following items 1-9, and its manufacturing method.
Item 1. A reactive fluorine-containing oligomer represented by the following general formula (1).

[Wherein, Rf represents a group represented by the following formula (2) or (3). R ¹ is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.) R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.) R ³ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). R ⁴ represents H or a methyl group. R ⁵ represents H or a monovalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). Or an aryl group. R ⁶ , R ⁷ and R ⁸ are each independently H or a methyl group. Each of n and p is an integer of 1 to 30, and m + q is an integer of 1 to 60. However, the order of each group of repeating units is not specified. x is an integer of 1 or 2. ]

Item 2. Item 2. The reactive fluorine-containing oligomer according to Item 1, having a weight average molecular weight of 2,000 to 50,000.
Item 3. The ratio between n and m + p + q is 0.1 ≦ n / (m + p + q) ≦ 10.0, the ratio between m and m + p is 0 ≦ m / (m + p) <1.0, and the ratio between q and n + m + p is The reactive fluorine-containing oligomer according to Item 1 or 2, wherein 0 ≦ q / (n + m + p) ≦ 5.0.
Item 4. R ^{1 in the} general formula (1) is a divalent saturated aliphatic hydrocarbon group having 2 to 30 carbon atoms (the saturated aliphatic hydrocarbon group optionally has an ether bond, an ester bond, an amide bond or an aryl group). The reactive fluorine-containing oligomer according to any one of Items 1 to 3, which may be
Item 5. R ^{2 in the} general formula (1) is a divalent saturated aliphatic hydrocarbon group having 2 to 50 carbon atoms (the saturated aliphatic hydrocarbon group may have an ether bond, an ester bond or an aryl group if desired) The reactive fluorine-containing oligomer according to any one of Items 1 to 3, which is good.
Item 6. R ^{3 in the} general formula (1) is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 5 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). Item 4. The reactive fluorine-containing oligomer according to any one of Items 1 to 3.
Item 7. R ^{5 in the} general formula (1) is H or a monovalent saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms (the saturated aliphatic hydrocarbon group is optionally a halogen atom, an ether bond, an ester bond, The reactive fluorine-containing oligomer according to any one of Items 1 to 3, which may have an amide bond or an aryl group.
Item 8. Item 8. A method for producing a reactive fluorine-containing oligomer according to any one of Items 1 to 7, wherein the following general formula (4):

[Wherein, Rf represents a group represented by the following formula (2) or (3). R ¹ is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.) R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.) R ⁵ represents H or a monovalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). Or an aryl group. R ⁶ , R ⁷ and R ⁸ are each independently H or a methyl group. Each of n and m is an integer of 1 to 30, and q is an integer of 0 to 30. However, the order of each group of repeating units is not specified. ]

And a hydroxyl group-containing fluorine-containing oligomer represented by the following general formula (5)

[Wherein R ³ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). It is. R ⁴ represents H or a methyl group. x is an integer of 1 or 2. ]
And a reactive compound having an isocyanate group at the terminal represented by the following reaction in an organic solvent in the presence of an alkaline catalyst.
Item 9. 1 mol of the hydroxyl group-containing fluorine-containing oligomer represented by the general formula (4) is reacted with 0.1 to 30 mol of a reactive compound having an isocyanate group at the terminal represented by the general formula (5). Item 9. The manufacturing method according to Item 8, wherein

  According to the present invention, it is useful as a surface modifier for resins, films, fibers, glass, metals, etc., and has reactive reactivity that can impart water and oil repellency, antifouling properties, and leveling properties to those surfaces. A fluorine oligomer is provided. Since the reactive fluorine-containing oligomer of the present invention has a reactive acrylate group or a methacrylate group in the molecule, it can be expected to have a high durability with a surface modification effect by enhancing adhesion using a chemical bond to the substrate surface. . Further, by controlling the amount of reactive groups in the molecule, reaction conditions, and the like, it is possible to improve the film strength as a surface modifier and to design the strength according to the purpose. Furthermore, the reactive fluorine-containing oligomer of the present invention can also improve the solubility in a solvent during surface modification by introducing a hydrocarbon-based substituent, a hydrophilic substituent or the like into the molecule.

Reactive fluorine-containing oligomer The reactive fluorine-containing oligomer of the present invention has the following general formula (1):

[Wherein, Rf represents a group represented by the following formula (2) or (3).
R ¹ is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.)
R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.)
R ³ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond).
R ⁴ represents H or a methyl group.
R ⁵ represents H or a monovalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). Or an aryl group.
R ⁶ , R ⁷ and R ⁸ are each independently H or a methyl group.
Each of n and p is an integer of 1 to 30, and m + q is an integer of 1 to 60. However, the order of each group of repeating units is not specified. x is an integer of 1 or 2. ]

It is a compound represented by these.

  In preferable embodiment of this invention, in said general formula (1), each of n and p is an integer of 1-30, m + q is an integer of 1-60, and the ratio of n and m + p + q is 0.00. 1 ≦ n / (m + p + q) ≦ 10.0 is preferable, and 0.1 ≦ n / (m + p + q) ≦ 8.0 is particularly preferable.

  The ratio of m to m + p is preferably 0 ≦ m / (m + p) <1.0, particularly preferably 0 ≦ m / (m + p) ≦ 0.9. The ratio of q to n + m + p is preferably 0 ≦ q / (n + m + p) ≦ 5.0, and particularly preferably 0 ≦ q / (n + m + p) ≦ 3.0.

R ¹ in the general formula (1) is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms, preferably 2 to 30 carbon atoms. The saturated aliphatic hydrocarbon group is optionally a halogen atom, an ether bond (—O—), an ester bond (—COO— or —O—CO—), an amide bond (—NHCO— or —CONH—) or an aryl group. You may have.

  In the present invention, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom. As an aryl group, C6-C15 aryl groups, such as a phenyl group, a naphthyl group, a toluyl group, a xylyl group, an anthranyl group, a phenanthryl group, are mentioned, for example.

In the general formula (1), particularly preferred R ^1, include divalent saturated aliphatic hydrocarbon group specifically the following structure.

_{- (CH 2) n1 - (} n1 = 2~10)
_{- (CH 2) n2 OCOC 6} H 4 - (n2 = 2~10)
_{- (CH 2) n3 C 6} H 4 - (n3 = 1~10)
_{- (CH 2 CH 2 O)} n4 CH 2 CH 2 - (n4 = 1~10)
_{- (CH 2 CH 2 O)} n5 COC 6 H 4 - (n5 = 1~10).

In the general formula (1), R ² is usually a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms, preferably 2 to 50 carbon atoms. The saturated aliphatic hydrocarbon group may optionally have a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group.

Particularly preferable R ² includes a divalent saturated aliphatic hydrocarbon group having the following structure.

_{- (CH 2) n6 - (} n6 = 2~10)
_{- (CH 2 CH 2 O)} n7 CH 2 CH 2 - (n7 = 1~20)
_{- (CH 2 CH 2 CH 2} O) n8 CH 2 CH 2 CH 2 - (n8 = 1~10).

In the general formula (1), R ³ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. The saturated aliphatic hydrocarbon group may optionally have an ether bond.

Preferred R ^3, specifically include the following groups.

R ⁴ in the general formula (1) is H or a methyl group.

R ⁵ in the general formula (1) is H or a monovalent saturated aliphatic hydrocarbon group or aryl group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms. The saturated aliphatic hydrocarbon group may optionally have a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group.

Specific examples of preferable R ⁵ include —H group, cyclohexyl group, isobornyl group, benzyl group, 2-ethylhexyl group, dicyclopentanyl group, isooctyl group, formula — (CH ₂ ) _n9 CH ₃ (n9 = 0-20), groups represented by the formula — (CH ₂ CH ₂ O) _n10 CH ₃ (n10 = 1 to 10), and the like.

R ⁶ , R ⁷ and R ^{8 in the} general formula (1) are each independently H or a methyl group. Moreover, in General formula (1), the order of each group of a repeating unit is not specified, and may be random or a block. x is an integer of 1 or 2.

  The weight average molecular weight of the reactive fluorine-containing oligomer represented by the general formula (1) is, for example, about 2,000 to 50,000, and particularly preferably about 2,500 to 30,000.

Production method of reactive fluorine-containing oligomer The production method of the reactive fluorine-containing oligomer represented by the general formula (1) of the present invention is represented by the following general formula (4).

[Wherein, Rf represents a group represented by the following formula (2) or (3).
R ¹ is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.)
R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.)
R ⁵ represents H or a monovalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). Or an aryl group.
R ⁶ , R ⁷ and R ⁸ are each independently H or a methyl group.
Each of n and m is an integer of 1 to 30, and q is an integer of 0 to 30. However, the order of each group of repeating units is not specified. ]

And a hydroxyl group-containing fluorine-containing oligomer represented by the following general formula (5)

[Wherein R ³ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). It is.
R ⁴ represents H or a methyl group. x is an integer of 1 or 2. ]
And a reactive compound having an isocyanate group at the terminal represented by the formula (1) is reacted in an organic solvent in the presence of an alkaline catalyst.

Rf, R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , n, m and q in the general formula (4) are the same as those of the compound represented by the general formula (1). is there. In the general formula (5), R ³ , R ⁴ and x are the same as those of the compound represented by the general formula (1). In general formula (4), the order of each group of the repeating unit is not specified, and may be random or block.

The hydroxyl group-containing fluorine-containing oligomer represented by the general formula (4) is, for example, the following formula (4A)
_{^{CH 2 = CR 6 -COO-R}} 1 -O-Rf (4A)
Wherein R ⁶ , R ¹ and Rf are as defined above.
A fluorine-containing monomer represented by the following formula (4B)
_{^{CH 2 = CR 7 -COO-R}} 2 -OH (4B)
Wherein R ⁷ and R ² are as defined above.
And a hydroxyl group-containing monomer represented by the following formula (4C)
_{^{CH 2 = CR 8 -COO-R}} 5 (4C)
(Wherein R ⁸ and R ⁵ are as defined above).
Is mixed at the ratio of n: m: q, a polymerization initiator (for example, azobisisobutyronitrile, benzoyl peroxide, etc.) is added in an appropriate amount, and at room temperature in the presence of a solvent. To 100 ° C. for about 1 to 24 hours. The mixing order of the formulas (4A), (4B) and (4C) is not particularly limited.

  The monomers represented by the formulas (4A), (4B) and (4C) can be obtained by known methods, and commercially available products can also be used.

  The weight average molecular weight of the hydroxyl group-containing fluorine-containing oligomer represented by the general formula (4) is, for example, about 2,000 to 50,000, and particularly preferably about 2,000 to 30,000.

  In the production method of the present invention, the hydroxyl group-containing fluorine-containing oligomer represented by the general formula (4) may be used singly or in combination of two or more.

  Moreover, what is necessary is just to use a conventionally well-known thing as the reactive compound which has an isocyanate group at the terminal represented by the said General formula (5), and can also obtain a commercial item. The compound represented by General formula (5) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  Although the organic solvent used for the manufacturing method of this invention will not be specifically limited if the said reaction advances, For example, an aprotic solvent is mentioned. Preferred examples of the aprotic solvent include dimethoxyethane, ethyl acetate, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, toluene, and propylene glycol monomethyl ether acetate. The organic solvent may be used alone or in combination of two or more.

  The alkaline catalyst is not particularly limited as long as the above reaction proceeds. Preferred alkaline catalysts include, for example, organic solvents such as triethylamine, tributylamine, pyridine, and 1,4-diazabicyclo [2.2.2] octane. An alkaline catalyst is mentioned. The alkaline catalyst is particularly preferably 1,4-diazabicyclo [2.2.2] octane. The alkaline catalyst may be used alone or in combination of two or more.

  In the production method of the present invention, a preferable reaction temperature is about −20 ° C. to 100 ° C., but about 20 ° C. to 90 ° C. is particularly preferable.

  In the production method of the present invention, 0.1 to 30 mol of a reactive compound having an isocyanate group at the terminal of the general formula (5) is added to 1 mol of the hydroxyl group-containing fluorine-containing oligomer represented by the general formula (4). About 0.2 to 20 mol, more preferably about 0.5 to 15 mol. The use ratio of the compound represented by the general formula (4) and the compound represented by the general formula (5) is appropriately determined according to the characteristics required for the compound represented by the general formula (1), which is the target product. You only have to set it.

  Moreover, the usage-amount of an alkaline catalyst is about 0.0001-0.5 mol normally with respect to 1 mol of hydroxyl-containing fluorine-containing oligomers represented by General formula (4), Preferably it is 0.001-0.1 mol. Degree.

  The usage-amount of an organic solvent is about 0.5-20 weight part normally with respect to 1 weight part of hydroxyl-containing fluorine-containing oligomer represented by General formula (4), Preferably it is about 1-10 weight part.

  In the production method of the present invention, the reaction time is not particularly limited, but is usually about 1 to 48 hours.

  The reactive fluorine-containing oligomer of the present invention thus obtained has a branched perfluorocarbon chain represented by the general formulas (2) and (3) in the molecule among the perfluorocarbon chains. The reactive fluorine-containing oligomer of the present invention has a high surface modification effect by having a large number of trifluoromethyl groups in the molecule that are effective in reducing the surface energy.

  Further, the fluorine-containing compound (hexafluoropropene trimer) which is a raw material of the branched perfluorocarbon chain represented by the general formulas (2) and (3) has a high degree of branching, is relatively inexpensive, and is practically used. It is a very useful fluorocarbon chain introducing agent or a raw material for its preparation.

Method of Use The reactive fluorine-containing oligomer of the present invention represented by the general formula (1) is, for example, toluene, xylene, diethyl ether, ethyl acetate, methyl ethyl ketone, acetone, acetonitrile, propionitrile, diethylene glycol monoethyl ether, diethylene glycol. It can be used as a solution of an organic solvent such as diethyl ether, ethanol, isopropanol, tetrahydrofuran, 1,4-dioxane, or as a solution added to a coating solution such as a paint.

  The reactive fluorine-containing oligomer of this invention represented by General formula (1) may be used individually by 1 type, and may mix and use 2 or more types. Moreover, the said solvent used for this solution may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  The above-mentioned solution containing the reactive fluorine-containing oligomer of the present invention is applied to the surface of a substrate such as resin, film, fiber, glass, metal, etc. by coating, coating, spraying, etc., thereby improving the properties of the substrate surface. Can be quality. That is, when the solvent in the solution evaporates, the reactive fluorine-containing oligomer film of the present invention is formed on the substrate surface. The film has water / oil repellency, antifouling property, leveling property and the like. The drying (evaporation) conditions of the solvent vary depending on the type and amount of the solvent in the solution, but are usually dried at room temperature to 200 ° C. for 10 seconds to 10 minutes.

Since the reactive fluorine-containing oligomer of the present invention has a reactive acrylate group or a methacrylate group in the molecule, it can be expected to have a high durability with a surface modification effect by enhancing adhesion using a chemical bond to the substrate surface. . That is, the acryl group or methacryl group, which is a reactive group in the reactive fluorine-containing oligomer of the present invention, reacts with the substrate surface and / or the reactive fluorine-containing oligomer itself, usually by light. Although this photoreaction differs depending on the conditions, it cannot be limited, but it can usually be achieved by irradiating light having a wavelength of about 250 nm to 400 nm with 100 to 500 mJ / cm ² . The photoreaction may be performed after the drying treatment. The photoreaction can also use sunlight in some cases. Thereby, the film | membrane of a fluorine-containing oligomer adheres on the base-material surface, and high sustainability, such as water / oil repellency, antifouling property, leveling property, is achieved.
Further, by controlling the amount of reactive groups in the fluorine-containing oligomer molecule, reaction conditions, and the like, it is possible to improve the film strength as a surface modifier and to design the strength according to the purpose.

  The concentration of the reactive fluorine-containing oligomer solution in the solution is not particularly limited, but may be, for example, about 0.1 to 90.0% by weight. If the concentration of the reactive fluorine-containing oligomer solution in the solution is too low, the amount of the reactive fluorine-containing oligomer present on the surface decreases, the coated or sprayed modified surface becomes thin, or the reactivity decreases. It becomes a factor. In addition, problems such as insufficient strength of the modified surface may occur. On the other hand, if the concentration is too high, uneven coating may occur. The concentration of the reactive fluorine-containing oligomer solution in the solution is also affected by the solubility depending on the type of solvent, the molecular weight of the polymer, and the like.

  Moreover, when using a photoinitiator, the usage-amount of a photoinitiator should just be about 0.01-10 weight% in this solution.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, it is not intending that this invention is limited to an Example.

Synthesis example 1
In a three-necked flask (3 L) equipped with a dropping funnel, 259.5 g (1.8 mol) of 4-hydroxybutyl acrylate, 218.6 g (2.16 mol) of triethylamine, and 1000 g of acetonitrile were placed. The dropping funnel was charged with 973.0 g (2.16 mol) of hexafluoropropene trimer and gradually dropped into the solution in the flask over about 60 minutes with stirring. After completion of the dropwise addition, stirring was continued for another 3 hours at room temperature.

To the reaction mixture, 2200 g of 1N hydrochloric acid was added to stop the reaction. Then, the reaction mixture was transferred into a 5 L beaker, and then washed with 1 L of water three times. The solution after the water washing treatment was dehydrated under reduced pressure to obtain 964.0 g (yield 93%) of a fluorinated acrylate represented by the following formula (6). Table 1 shows the ¹ H-NMR data of the resulting fluorinated acrylate (6).

[Wherein Rf is a group represented by the following general formula (2) or (3). ]

Synthesis example 2
In a three-necked flask (3 L) equipped with a dropping funnel, 130.1 g (1.0 mol) of 2-hydroxyethyl methacrylate, 111.1 g (1.1 mol) of triethylamine, and 600 g of ethyl acetate were put. In a dropping funnel, 586.5 g (1.0 mol) of a fluorine-containing acid chloride represented by the following formula (7) and 100 g of ethyl acetate were placed, and gradually dropped into the solution in the flask over about 60 minutes with stirring. After completion of the dropwise addition, stirring was continued for another 3 hours at room temperature.

The reaction mixture was added with 1050 g of 1N hydrochloric acid to stop the reaction, and then the reaction mixture was transferred into a 3 L beaker, and then washed with 1 L of water three times. The solution after the water washing treatment was dehydrated under reduced pressure to obtain 634.8 g (yield 93%) of fluorinated methacrylate represented by the following formula (8). Table 2 shows ¹ H-NMR data of the obtained fluorinated methacrylate (8).

[Wherein Rf is a group represented by the following general formula (3). ]

[Wherein Rf is the following general formula (3). ]

Synthesis example 3
In a three-necked flask (2 L) equipped with a condenser tube, 287.1 g (0.5 mol) of the fluorine-containing acrylate (6) synthesized in Synthesis Example 1, Bremer AE-400 [HO (CH ₂ CH ₂ O) ₁₀ C (═O) CH═CH ₂ ] 256.1 g (0.5 mol), ethyl acetate 543.2 g, 2,2′-azobisisobutyronitrile 4.8 g (29.3 mmol), lauryl 41.5 g (204.8 mmol) of mercaptan was added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. while stirring the reaction solution to start the reaction. Thereafter, stirring was continued at 80 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of the peak specific to each acrylate in ¹ H-NMR. The objective hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 1132.7 g, 50 mass% ethyl acetate solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). Table 3 shows the measurement results.

Synthesis example 4
In a three-necked flask (200 mL) equipped with a condenser tube, 28.71 g (0.05 mol) of the fluorine-containing acrylate (6) synthesized in Synthesis Example 1 and 21.64 g (0.15 mol) of 4-hydroxybutyl acrylate, 51.02 g of ethyl acetate, 0.96 g (5.85 mmol) of 2,2′-azobisisobutyronitrile and 8.91 g (43.88 mmol) of lauryl mercaptan were added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. while stirring the reaction solution to start the reaction. Thereafter, stirring was continued at 80 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of the peak specific to each acrylate in ¹ H-NMR. The objective hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 111.24 g, 50 mass% ethyl acetate solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis example 5
In a three-necked flask (200 mL) equipped with a condenser tube, 34.17 g (0.05 mol) of the fluorine-containing methacrylate (8) synthesized in Synthesis Example 2, 7.27 g (0.05 mol) of 4-hydroxybutyl acrylate, 41.45 g of ethyl acetate, 0.48 g (2.93 mmol) of 2,2′-azobisisobutyronitrile and 4.14 g (20.48 mmol) of lauryl mercaptan were added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 80 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of peaks specific to each acrylate and methacrylate in ¹ H-NMR. The objective hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 87.51 g, 50 mass% ethyl acetate solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis Example 6
In a three-necked flask (200 mL) equipped with a condenser tube, 17.22 g (0.03 mol) of the fluorine-containing acrylate (6) synthesized in Synthesis Example 1, Bremermer AE-400 manufactured by NOF Corporation, 15.38 g (0 0.03 mol), NOF Blemmer LA [CH ₃ (CH ₂ ) ₁₁ OC (═O) CH═CH ₂ ], 14.42 g (0.06 mol), ethyl acetate 47.12 g, 2,2′-azo Bisisobutyronitrile 0.58 g (3.51 mmol) and lauryl mercaptan 3.56 g (17.55 mmol) were added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. while stirring the reaction solution to start the reaction. Thereafter, stirring was continued at 80 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of the peak specific to each acrylate in ¹ H-NMR. The objective hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 98.28 g, 50 mass% ethyl acetate solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis example 7
In a three-necked flask (2 L) equipped with a condenser tube, 258.88 g (0.45 mol) of the fluorine-containing acrylate (6) synthesized in Synthesis Example 1 and 230.93 g (0 .45 mol), 490.81 g of ethyl acetate, 4.32 g (26.3 mmol) of 2,2′-azobisisobutyronitrile, and 11.75 g (57.92 mmol) of lauryl mercaptan were added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. while stirring the reaction solution to start the reaction. Thereafter, stirring was continued at 80 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of the peak specific to each acrylate in ¹ H-NMR. The objective hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 996.69 g, 50 mass% ethyl acetate solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis Example 8
In a three-necked flask (200 mL) equipped with a condenser tube, 8.95 g (13.1 mmol) of the fluorine-containing methacrylate (8) synthesized in Synthesis Example 2, 10.37 g (71.9 mmol) of 4-hydroxybutyl acrylate, Methacrylic acid 0.61 g (7.1 mmol), propylene glycol monomethyl ether acetate 30.0 g, 2,2′-azobisisobutyronitrile 0.15 g (0.92 mmol), lauryl mercaptan 0.16 g (0.79 mmol) Put. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of peaks specific to each acrylate and methacrylate in ¹ H-NMR. The objective hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 50.24 g, 40 mass% propylene glycol monomethyl ether acetate solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis Example 9
In a three-necked flask (200 mL) equipped with a condenser tube, 9.56 g (14.0 mmol) of the fluorine-containing methacrylate (8) synthesized in Synthesis Example 2, 10.27 g (71.2 mmol) of 4-hydroxybutyl acrylate, 1.34 g (15.5 mmol) of methacrylic acid, 30.0 g of propylene glycol monomethyl ether acetate, 0.15 g (0.91 mmol) of 2,2′-azobisisobutyronitrile, 0.15 g (0.74 mmol) of lauryl mercaptan Put. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 90 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 90 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of peaks specific to each acrylate and methacrylate in ¹ H-NMR. The target hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 51.47 g, 41.7 mass% propylene glycol monomethyl ether acetate solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis Example 10
In a three-necked flask (200 mL) equipped with a condenser, 6.80 g (10.0 mmol) of the fluorine-containing methacrylate (8) synthesized in Synthesis Example 2, 1.48 g (10.0 mmol) of 4-hydroxybutyl acrylate, 4.80 g (20.0 mmol) of lauryl acrylate, 13.0 g of dimethoxyethane, 0.0673 g (0.41 mmol) of 2,2′-azobisisobutyronitrile, and 0.20 g (0.99 mmol) of lauryl mercaptan were added. . Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 80 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of peaks specific to each acrylate and methacrylate in ¹ H-NMR. The objective hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 26.35 g, 50.7 mass% dimethoxyethane solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis Example 11
In a three-necked flask (200 mL) equipped with a condenser tube, 6.80 g (10.0 mmol) of the fluorine-containing methacrylate (8) synthesized in Synthesis Example 2, 1.45 g (10.0 mmol) of 4-hydroxybutyl acrylate, 7.04 g (40.0 mmol) of benzyl acrylate, 15.3 g of dimethoxyethane, 0.102 g (0.61 mmol) of 2,2′-azobisisobutyronitrile, and 0.30 g (1.48 mmol) of lauryl mercaptan were added. . Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. with stirring to initiate the reaction. Thereafter, stirring was continued at 80 ° C. for 14 hours. The completion of the reaction was confirmed by disappearance of peaks specific to each acrylate and methacrylate in ¹ H-NMR. The target hydroxyl group-containing fluorine-containing oligomer was quantitatively obtained (yield 30.99 g, 49.4 mass% dimethoxyethane solution).

  The weight average molecular weight of the obtained hydroxyl-containing fluorine-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Synthesis Comparative Example 1
In a three-necked flask (200 mL) equipped with a condenser tube, NOF BLEMER AE-400, 51.2 g (0.1 mol), ethyl acetate 51.2 g, 2,2′-azobisisobutyronitrile 1.64 g (10 mmol) and 6.07 g (30 mmol) of lauryl mercaptan were added. Nitrogen gas was introduced into the reaction solution, and the inside of the reaction vessel was purged with nitrogen. After nitrogen substitution, the reaction solution was heated to 80 ° C. while stirring the reaction solution to start the reaction. Thereafter, stirring was continued at 80 ° C. for 21 hours. The completion of the reaction was confirmed by disappearance of a peak specific to acrylate of ¹ H-NMR. The target comparative oligomer was obtained quantitatively (yield 110.11 g, 53.3% by mass ethyl acetate solution).

  The weight average molecular weight of the obtained hydroxyl group-containing oligomer was confirmed using GPC. Table 3 shows the measurement results.

Example 1
In the eggplant flask (50 ml) subjected to nitrogen substitution, the hydroxyl group-containing fluorine-containing oligomer synthesized in Synthesis Example 3 prepared in 50% by mass with ethyl acetate (in the compound represented by the general formula (4), R ¹ There _{- (CH 2) 4 -,} R 2 is _{- (CH 2 CH 2 O)} 9 CH 2 CH 2 -, compounds ^{R 6} and ^{R 7} is H, q is 0, m / n is 1) 20. 00 g, 0.712 g of 2- (isocyanatoethyl) methacrylate and 0.010 g of 1,4-diazabicyclo [2.2.2] octane were added. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 12 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 20.72 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5.

  0.06 g of photoinitiator (Irgacure 819 manufactured by Ciba Specialty Chemicals) was added to 3.00 g (50% by weight ethyl acetate solution) of the synthesized reactive fluorine-containing oligomer, and used after degreasing the glass plate (100 mm × 100 mm × 2 mm, acetone) ) Was coated at 1000 rpm for 10 seconds using a spin coater (Mikasa 1H07). Then, after drying at 90 ° C. for 60 seconds, UV irradiation (254 nm, 20 minutes) (UVP CL1000) is cured and the surface state is confirmed by tactile sensation, and the contact angle of water is Dropmaster 700 manufactured by Kyowa Interface Science Co., Ltd. And measured. The measurement results are shown in Table 6.

Example 2
In the eggplant flask (50 ml) subjected to nitrogen substitution, the hydroxyl group-containing fluorine-containing oligomer synthesized in Synthesis Example 4 prepared in 50% by mass with ethyl acetate (in the compound represented by the general formula (4), R ¹ Is — (CH ₂ ) ₄ —, R ² is — (CH ₂ ) ₄ —, R ⁶ and R ⁷ are H, q is 0, and m / n is 3) 10.00 g, 2- (isocyanatoethyl) ) 2.304 g of methacrylate and 0.017 g of 1,4-diazabicyclo [2.2.2] octane. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 40 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 12.32 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Further, the synthesized reactive fluorine-containing oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

Example 3
Hydroxyl-containing fluorine-containing oligomer synthesized in Synthesis Example 5 prepared in 50% by mass with ethyl acetate in an eggplant flask (50 ml) subjected to nitrogen substitution (in the compound represented by the general formula (4), R ¹ Is — (CH ₂ ) ₂ OCOC ₆ H ₄ —, R ² is — (CH ₂ ) ₄ —, R ⁶ is CH ₃ , R ⁷ is H, q is 0, and m / n is 1. 00 g, 0.216 g of 2- (isocyanatoethyl) methacrylate and 0.007 g of 1,4-diazabicyclo [2.2.2] octane were added. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 5 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 10.22 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Furthermore, the synthesized reactive fluorine-containing oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

Example 4
In a eggplant flask (50 ml) subjected to nitrogen substitution, the hydroxyl group-containing fluorine-containing oligomer synthesized in Synthesis Example 7 prepared in 50% by mass with ethyl acetate (in the compound represented by the general formula (4), R ¹ There _{- (CH 2) 4 -,} R 2 is _{- (CH 2 CH 2 O)} 9 CH 2 CH 2 -, compounds ^{R 6} and ^{R 7} is H, q is 0, m / n is 1) 20. 00 g, 0.725 g of 2- (isocyanatoethyl) methacrylate and 0.011 g of 1,4-diazabicyclo [2.2.2] octane were added. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 12 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 20.74 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Furthermore, the synthesized reactive fluorine-containing oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

Example 5
Hydroxyl-containing fluorine-containing oligomer synthesized in Synthesis Example 8 prepared in 20% by mass with propylene glycol monomethyl ether acetate in an eggplant flask (50 ml) subjected to nitrogen substitution (in the compound represented by the general formula (4)) , R ¹ is — (CH ₂ ) ₂ OCOC ₆ H ₄ —, R ² is — (CH ₂ ) ₄ —, R ⁵ is H, R ⁶ is CH ₃ , R ⁷ is H, R ⁸ is CH ₃ , ( m + q) / n is 6.0 and q / m is 0.1)) 10.00 g, 2- (isocyanatoethyl) methacrylate 0.224 g and 1,4-diazabicyclo [2.2.2] octane 01 g was added. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 4 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 10.225 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Furthermore, the synthesized reactive fluorine-containing oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

Example 6
Hydroxyl-containing fluorine-containing oligomer synthesized in Synthesis Example 9 (in the compound represented by the above general formula (4)) prepared in propylene glycol monomethyl ether acetate to 20% by mass in an eggplant flask (50 ml) subjected to nitrogen substitution , R ¹ is — (CH ₂ ) ₂ OCOC ₆ H ₄ —, R ² is — (CH ₂ ) ₄ —, R ⁵ is H, R ⁶ is CH ₃ , R ⁷ is H, R ⁸ is CH ₃ , ( compound in which m + q) / n is 6.2 and q / m is 0.22) 10.00 g, 1.05 g of 2- (isocyanatoethyl) methacrylate and 1,4-diazabicyclo [2.2.2] octane. 01 g was added. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 21 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 11.06 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Furthermore, the synthesized reactive fluorine-containing oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

Example 7
In the eggplant flask (50 ml) subjected to nitrogen substitution, the hydroxyl group-containing fluorine-containing oligomer synthesized in Synthesis Example 10 prepared in 50% by mass with dimethoxyethane (in the compound represented by the general formula (4), R ¹ Is — (CH ₂ ) ₂ OCOC ₆ H ₄ —, R ² is — (CH ₂ ) ₄ —, R ⁵ — (CH ₂ ) ₁₁ CH ₃ , R ⁶ is CH ₃ , R ⁷ is H, and R ⁸ is H , (M + q) / n is 3, and q / m is 2) 10.01 g, 2- (isocyanatoethyl) methacrylate 0.124 g and 1,4-diazabicyclo [2.2.2] octane 0.004 g I put it in. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 19 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 10.14 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Furthermore, the synthesized reactive fluorine-containing oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

Example 8
In the eggplant flask (50 ml) subjected to nitrogen substitution, the hydroxyl group-containing fluorine-containing oligomer synthesized in Synthesis Example 11 prepared in 50% by mass with dimethoxyethane (in the compound represented by the general formula (4), R ¹ Is — (CH ₂ ) ₂ OCOC ₆ H ₄ —, R ² is — (CH ₂ ) ₄ —, R ⁵ is —CH ₂ C ₆ H ₅ , R ⁶ is CH ₃ , R ⁷ is H, and R ⁸ is H. , (M + q) / n = 5, q / m = 4) 10.01 g, 2- (isocyanatoethyl) methacrylate 0.251 g and 1,4-diazabicyclo [2.2.2] octane 0.004 g I put it in. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 24 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 10.26 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Furthermore, the synthesized reactive fluorine-containing oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

Example 9
Hydroxyl-containing fluorine-containing oligomer synthesized in Synthesis Example 8 prepared in 20% by mass with propylene glycol monomethyl ether acetate in an eggplant flask (50 ml) subjected to nitrogen substitution (in the compound represented by the general formula (4)) , R ¹ is — (CH ₂ ) ₂ OCOC ₆ H ₄ —, R ² is — (CH ₂ ) ₄ —, R ⁵ is H, R ⁶ is CH ₃ , R ⁷ is H, R ⁸ is CH ₃ , ( m + q) / n is 6.0, and q / m is 0.1)) 10.00 g, 1,1-bis (acryloyloxymethyl) ethyl isocyanate 0.38 g and 1,4-diazabicyclo [2.2. 2] 0.009 g of octane was added. Thereafter, stirring of the reaction solution was continued at 80 ° C. for 9 hours. The completion of the reaction was confirmed using FT-IR. The objective reactive fluorine-containing oligomer was obtained quantitatively (yield 10.389 g).

  Table 4 shows the FT-IR data of the synthesized reactive fluorine-containing oligomer. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Furthermore, the synthesized reactive fluorine-containing oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

Comparative Example 1
Hydroxyl-containing fluorine-containing oligomer synthesized in Synthesis Example 3 prepared in 50% by mass with ethyl acetate used in Example 1 (in the compound represented by the general formula (4), R ¹ is — (CH ₂ ) ₄ −, R ² is — (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ —, R ⁶ is H, q is 0, and m / n is 1), 3.00 g is weighed, and a glass plate (100 mm × 100 mm × 2 mm, used after degreasing acetone) was subjected to coating treatment at 1000 rpm for 10 seconds using a spin coater (1H07 manufactured by Mikasa). Then, after drying at 90 ° C. for 60 seconds, UV irradiation (254 nm, 20 minutes) (UVP CL1000) is cured and the surface state is confirmed by touch, and the contact angle of water is Dropmaster 700 manufactured by Kyowa Interface Science Co., Ltd. And measured. The measurement results are shown in Table 6.

Comparative Example 2
As Comparative Example 2, the contact angle of water on a glass plate only degreased with acetone was measured using a DropMaster 700 manufactured by Kyowa Interface Science Co., Ltd. The measurement results are shown in Table 6.

Comparative Example 3
In the eggplant flask (50 ml) subjected to nitrogen substitution, the oligomer synthesized in Comparative Synthesis Example 1 prepared to 20% by mass with ethyl acetate (in the compound represented by the general formula (4), R ² is-( CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ —, a compound in which R ⁷ is H, n and q are 0) 8.00 g, 2- (isocyanatoethyl) methacrylate 0.101 g and 1,4-diazabicyclo [2. 2.2] 0.004 g of octane was added. Thereafter, stirring of the reaction solution was continued at 50 ° C. for 13 hours. The completion of the reaction was confirmed using FT-IR. A comparative reactive oligomer was obtained quantitatively (yield 8.105 g).

  Table 4 shows the FT-IR data of the synthesized reactive oligomers. The weight average molecular weight was confirmed using GPC, and the measurement results are shown in Table 5. Furthermore, the synthesized reactive oligomer was treated in the same manner as in Example 1, and the contact angle of water was measured. The measurement results are shown in Table 6.

  In the examples, the cured film treatment on the glass surface was possible with the surface state solidified (including gel). All of the contact angles of the examples were higher than those of the untreated glass plate of Comparative Example 2, indicating a hydrophobic effect on the glass surface. Comparative Example 1 was a fluorine-containing oligomer not imparted with reactivity, and a cured film treatment on the glass surface could not be performed. Comparative Example 3 is a fluorine-free reactive oligomer, and a cured film treatment on the glass surface was possible, but the glass surface could not be hydrophobized.

  The reactive fluorine-containing oligomer according to the present invention is useful as a surface modifier for, for example, glass and film, and is useful as a compound that can impart water and oil repellency and antifouling properties to the film surface.

Claims (9)

A reactive fluorine-containing oligomer represented by the following general formula (1).

[Wherein, Rf represents a group represented by the following formula (2) or (3). R ¹ is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.) R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.) R ³ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). R ⁴ represents H or a methyl group. R ⁵ represents H or a monovalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). Or an aryl group. R ⁶ , R ⁷ and R ⁸ are each independently H or a methyl group. Each of n and p is an integer of 1 to 30, and m + q is an integer of 1 to 60. However, the order of each group of repeating units is not specified. x is an integer of 1 or 2. ]

  The reactive fluorine-containing oligomer according to claim 1, which has a weight average molecular weight of 2,000 to 50,000.   The ratio between n and m + p + q is 0.1 ≦ n / (m + p + q) ≦ 10.0, the ratio between m and m + p is 0 ≦ m / (m + p) <1.0, and the ratio between q and n + m + p is The reactive fluorine-containing oligomer according to claim 1, wherein 0 ≦ q / (n + m + p) ≦ 5.0. R ^{1 in the} general formula (1) is a divalent saturated aliphatic hydrocarbon group having 2 to 30 carbon atoms (the saturated aliphatic hydrocarbon group optionally has an ether bond, an ester bond, an amide bond or an aryl group). The reactive fluorine-containing oligomer according to any one of claims 1 to 3. R ^{2 in the} general formula (1) is a divalent saturated aliphatic hydrocarbon group having 2 to 50 carbon atoms (the saturated aliphatic hydrocarbon group may have an ether bond, an ester bond or an aryl group if desired) The reactive fluorine-containing oligomer according to any one of claims 1 to 3. R ^{3 in the} general formula (1) is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 5 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). The reactive fluorine-containing oligomer according to any one of claims 1 to 3. R ^{5 in the} general formula (1) is H or a monovalent saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms (the saturated aliphatic hydrocarbon group is optionally a halogen atom, an ether bond, an ester bond, The reactive fluorine-containing oligomer according to claim 1, which may have an amide bond or an aryl group.) Or an aryl group. It is a manufacturing method of the reactive fluorine-containing oligomer in any one of Claims 1-7, Comprising: The following general formula (4)

[Wherein, Rf represents a group represented by the following formula (2) or (3). R ¹ is a divalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.) R ² is a divalent saturated aliphatic hydrocarbon group having 1 to 100 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). It is good.) R ⁵ represents H or a monovalent saturated aliphatic hydrocarbon group having 1 to 50 carbon atoms (the saturated aliphatic hydrocarbon group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group). Or an aryl group. R ⁶ , R ⁷ and R ⁸ are each independently H or a methyl group. Each of n and m is an integer of 1 to 30, and q is an integer of 0 to 30. However, the order of each group of repeating units is not specified. ]

And a hydroxyl group-containing fluorine-containing oligomer represented by the following general formula (5)

[Wherein R ³ is a divalent or trivalent saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms (the saturated aliphatic hydrocarbon group may optionally have an ether bond). It is. R ⁴ represents H or a methyl group. x is an integer of 1 or 2. ]
And a reactive compound having an isocyanate group at the terminal represented by the following reaction in an organic solvent in the presence of an alkaline catalyst.   1 mol of the hydroxyl group-containing fluorine-containing oligomer represented by the general formula (4) is reacted with 0.1 to 30 mol of a reactive compound having an isocyanate group at the terminal represented by the general formula (5). The manufacturing method according to claim 8.