JP5674404B2 - Fluorine-containing surface conditioner - Google Patents

Description

  The present invention relates to a fluorine-containing graft copolymer having a perfluoroalkenyl group, which is useful as a surface modifier used in the fields of resins, optical materials, paints and the like.

  Coating liquids used in the fields of resins, optical materials, paints and the like include a coating process on the member surface. Functions such as water and oil repellency to the coating film surface for the purpose of suppressing defects such as streaks, repellency, unevenness, irregularities, and non-wetting, that is, imparting smoothness to the coating film surface. Various substances have been added to the coating liquid for the purpose of imparting properties.

  A compound containing a perfluoroalkenyl group is also used as an additive in this application, and in particular, a nonionic surfactant having a perfluoroalkenyl group is known to be useful in terms of imparting surface smoothness. (For example, Patent Document 1).

  Examples of the copolymer used as the fluorosurfactant include a random copolymer of a fluorine-containing monomer and a monomer having a philic group. However, coating liquids containing a fluorocopolymer, which is a random copolymer, have excellent surface smoothness, but may not be low in foaming properties and may lead to deterioration in operability and coating quality. there were. In addition, when the fluorine content is small, the random copolymer is poor in surface tension and tends to have poor surface smoothness and water / oil repellency on the surface of the coating film. In order to exhibit the function as a leveling agent, it was necessary to increase the fluorine content or the amount added to the coating liquid.

JP 2008-77057 A

  The main object of the present invention is to provide a novel fluorine-containing surface conditioner that solves the above-mentioned problems of the prior art.

  As a result of intensive studies to solve these problems, the present inventor has found that the fluorine-containing graft copolymer in which at least one of the branch polymer and the trunk polymer contains a fluoroalkyl group has a low foam property and a random copolymer. It has excellent ability to reduce surface tension even when the fluorine monomer ratio is lower than that of the polymer, and it is possible to impart surface smoothness and water / oil repellency to the coating surface when a coating material is applied. I found it.

Based on these findings, the present invention has been completed through further studies. That is, the present invention relates to the fluorine-containing surface conditioner according to items 1 to 8 below.
Item 1.
A fluorine-containing graft copolymer comprising a (meth) acrylic acid ester represented by the following monomer (1), monomer (2) and monomer (3), wherein at least one of a branch polymer and a trunk polymer: A fluorine-containing surface conditioner comprising a graft copolymer containing a structural unit composed of a fluorine-containing monomer represented by the following monomer (1).

[Wherein Rf is a formula represented by the following formula (4) or (5). R ¹ is a divalent linking group having 1 to 50 carbon atoms (the linking group may optionally have a halogen atom, an ether bond, an ester bond, an amide bond or an aryl moiety).
R ³ is an organic group having 1 to 50 carbon atoms (the organic group may optionally have a halogen atom, an ether bond, an ester bond, an amide bond or an aryl moiety).
R ⁵ is a divalent linking group having 1 to 100 carbon atoms (the linking group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl moiety).
R ² , R ⁴ and R ⁶ are each independently H or a methyl group. ]

Item 2.
A term comprising a graft copolymer obtained by graft polymerization of a fluorine-containing monomer represented by monomer (1) to a trunk polymer obtained by copolymerization of monomer (2) and monomer (3). 1. The fluorine-containing surface conditioner according to 1.
Item 3.
Item 3. The fluorine-containing surface modifier according to Item 1 or 2, wherein the weight average molecular weight of the trunk polymer in the fluorine-containing graft copolymer is 2,000 to 50,000.
Item 4.
Item 4. The fluorine-containing surface conditioner according to item 1, 2 or 3, wherein the fluorine-containing graft copolymer has a weight average molecular weight of 2,000 to 100,000.
Item 5.
In the fluorine-containing graft copolymer, the weight ratio of the total amount of monomer (1), monomer (2) and monomer (3) is monomer (1): monomer (2 ) And the total amount of the monomer (3) = 1: 99 to 55:45.
Item 6.
In the monomer (1), R ¹ is a divalent linking group having 2 to 30 carbon atoms (this linking group may optionally have an ether bond, an ester bond, an amide bond or an aryl moiety). Item 6. The fluorine-containing surface conditioner according to item 1, 2, 3, 4 or 5.
Item 7.
Item 1, wherein R ³ in the monomer (2) is an organic group having 1 to 30 carbon atoms (the linking group may optionally have an ether bond, an ester bond, an amide bond or an aryl moiety). The fluorine-containing surface conditioner according to 2, 3, 4, 5, or 6.
Item 8.
In the monomer (3), R ⁵ is a divalent linking group having 2 to 50 carbon atoms (this linking group may optionally have an ether bond, an ester bond, an amide bond or an aryl moiety). Item 8. The fluorine-containing surface conditioner according to Item 1, 2, 3, 4, 5, 6 or 7.

  Since the fluorine-containing graft copolymer of the present invention has the above-mentioned special perfluoro site, it suppresses streaks, repellency, unevenness, unevenness, non-wetting, etc. in the coating liquid coating process, that is, to the coating film surface. Smoothness is imparted. Although the organic fluorine compound has a problem of environmental burden due to its low degradability, according to the present invention, a fluorine-containing surface conditioner having excellent surface smoothness and low foaming properties has been conventionally used (random copolymer). ) Can be produced with a smaller fluorine monomer ratio.

  Hereinafter, the fluorine-containing surface conditioner of the present invention will be described in detail. The fluorine-containing oligomer of the present invention is a fluorine-containing graft copolymer comprising (meth) acrylic acid ester represented by the following monomer (1) monomer (2) and monomer (3), At least one of the polymer and the backbone polymer contains a graft copolymer containing a constitutional unit composed of a fluorine-containing monomer represented by the following monomer (1).

Monomer (1)
R ¹ of the fluorine-containing (meth) acrylic acid ester represented by the monomer (1) is a divalent linking group having 1 to 50 carbon atoms, preferably 2 to 30 carbon atoms (the linking group). The group may optionally have a halogen atom, an ether bond (—O—), an ester bond (—COO— or —O—CO—), an amide bond (—NHCO— or —CONH—) or an aryl moiety. .)

  In the present specification, 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, and examples of the aryl moiety include phenyl (phenylene) and naphthyl (naphthylene). , Aryl groups or arylene groups having 6 to 15 carbon atoms such as toluyl (toluylene), xylyl (xylylene), anthranyl (anthranylene), phenanthryl (phenanthrylene), and the like.

Preferable R ¹ specifically includes a divalent linking group having the following structure.
− (CH ₂ ) _n1 − (n1 = 2 to 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)

R ² is H or a methyl group.

  In this invention, this monomer (1) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

Monomer (2)
In the (meth) acrylic acid ester represented by the monomer (2), R ³ is usually an organic group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms. The organic group may optionally have a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group.

Preferred examples of R ³ include the following substituents.
_{- (CH 2) n9 CH 3} (n9 = 0~20)
_{- (CH 2 CH 2 O)} n10 CH 3 (n10 = 1~10)

R ⁴ is H or a methyl group.

  In this invention, this monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

Monomer (3)
In the (meth) acrylic acid ester represented by the monomer (3), R ⁵ is a divalent linking group having usually 1 to 100 carbon atoms, preferably 2 to 50 carbon atoms. The linking group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl group.

Particularly preferable R ⁵ includes a divalent linking 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)

R ⁶ is H or a methyl group.

  In this invention, this monomer may be used individually by 1 type, and 2 or more types may be mixed and used for it.

Fluorine-containing graft copolymer In the fluorine-containing graft copolymer of the present invention, the monomer (1) is contained in at least one of a trunk polymer or a branch polymer, preferably at least in a branch polymer. When monomer (1) is contained in the branch polymer rather than contained in the trunk polymer, it is more effective in suppressing streaks, repellency, unevenness, unevenness, non-wetting, etc., that is, smoothness to the coating film surface. Is granted.

  In addition, when the trunk polymer is a copolymer of two or more types of monomers, the trunk polymer may be either a random copolymer or a block copolymer.

  Preferred monomer combinations of the fluorine-containing graft copolymer of the present invention are as follows.

  The fluorine-containing graft copolymer of the present invention is about 20 to 80% by weight of the trunk polymer and about 20 to 80% by weight of the branch polymer, and the ratio of the branch polymer / the trunk polymer is about 1: 0.25 to 1:10. is there.

  The ratio of the monomers (1) to (3) is such that when the entire copolymer is 100% by mass, the monomer (1) is 1 to 55% by mass, and the monomer (2) is a single amount. The total amount of the body (3) is 45 to 99% by mass; preferably the monomer (1) is 1 to 45% by mass, and the total amount of the monomer (2) and the monomer (3) is 55 to 99% by mass. More preferably, the monomer (1) is 1 to 30% by mass, and the total amount of the monomer (2) and the monomer (3) is 70 to 99% by mass. When the amount of the monomer (1) is excessive, the above range is preferable because the solubility in the liquid medium is deteriorated.

  The weight average molecular weight of the backbone polymer of the fluorine-containing graft copolymer is about 2,000 to 50,000, preferably about 4,000 to 20,000.

  The weight average molecular weight of the fluorine-containing graft copolymer is about 2,000 to 100,000, preferably about 4,000 to 30,000.

  The graft copolymer of the present invention can be copolymerized with other monomers as long as the effects of the present invention are not impaired. The usage-amount of another monomer is about 0-10 mass% of the whole copolymer.

Other monomers include the following:
Styrene, butadiene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, vinyl acetate, butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, and the like.

  The trunk polymer can be obtained from a monomer selected from monomer (1), monomer (2) and monomer (3) by a solution polymerization method, an emulsion polymerization method, a bulk polymerization method or the like. For example, in the case of a solution polymerization method, the main polymer can be obtained by dissolving each monomer in a solvent with a desired composition and heating it using a radical polymerization initiator in a nitrogen atmosphere.

  As the solvent used in the polymerization, any solvent can be used as long as it dissolves or suspends the monomer (1), the monomer (2) and the monomer (3). For example, there are water or toluene, heptane, cyclohexane, ethyl acetate, acetonitrile, N, N-dimethylformamide, tetrahydrofuran, etc., and these can be used alone or in combination of two or more.

  A preferred graft copolymer of the present invention can be prepared by graft polymerization of a (meth) acrylic acid ester containing the monomer (1) to the trunk polymer obtained as described above by a known polymerization method. it can. For example, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk polymerization method and the like can be used, but a solution polymerization method is preferable because it can be performed with a relatively simple apparatus.

  Solution polymerization is carried out by dissolving the reaction components in a suitable solvent and adding an organic peroxide or irradiating with ionizing radiation.

  The organic peroxide is not particularly limited. For example, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl cumer peroxide, di-t-butyl peroxide, benzoyl peroxide, diisobutyl peroxide, bis ( 4-t-butylcyclohexyl) peroxydicarbonate, diisopropanol peroxydicarbonate and the like can be widely used. These peroxides may be used alone or in combination of two or more.

  In this graft polymerization, a monomer selected from the monomer (1), the monomer (2), and the monomer (3) and an initiator are put into the reaction solvent for synthesizing the trunk polymer. You may go. Alternatively, the trunk polymer may be once taken out from the reaction solvent, and the trunk polymer is dissolved again in the solvent to form a solution, and the monomer and initiator may be put into this solution.

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

  The fluorine-containing graft oligomer of the present invention thus obtained has a branched perfluorocarbon represented by the general formulas (4) and (5) in the molecule among the perfluorocarbon chains. The fluorine-containing oligomer of the present invention has a high surface modification effect by having a large number of trifluoromethyl groups in the molecule, which is effective for lowering the surface energy. For example, streaks, repels, Suppression of unevenness, unevenness, non-wetting, etc., that is, smoothness to the coating film surface is imparted.

  Further, the fluorine-containing compound (hexafluoropropene trimer) which is a raw material for the branched perfluorocarbon chain represented by the general formulas (4) and (5) 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 adjusting the same.

Method of Use The fluorine-containing graft oligomer of the present invention includes, for example, aromatic hydrocarbons such as toluene and xylene, ethers such as diethyl ether, esters such as ethyl acetate, ketones such as methyl ethyl ketone and acetone, acetonitrile, propionitrile Nitriles such as, alkylene glycol monoethers such as diethylene glycol monoethyl ether, alkylene glycol diethers such as diethylene glycol diethyl ether, lower alcohols such as methanol, ethanol and isopropanol, organic solvents such as tetrahydrofuran and 1,4-dioxane Or as a solution added to a coating liquid such as a resin, an optical material, or a paint.

  The fluorine-containing graft copolymer obtained from the monomer (1), monomer (2) and monomer (3) may be used alone or in combination of two or more. May be. Moreover, the said solvent used for this solution may be used individually by 1 type, and may mix 2 or more types.

  The solution containing the fluorine-containing graft copolymer 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 fluorine-containing graft oligomer film of the present invention is formed on the substrate surface. The solution containing the fluorine-containing graft copolymer is preferably applied as a solution having a concentration of 5% by mass or less, preferably 3% by mass or less, for example, ˜2%.

  The film has water / oil repellency, antifouling property, leveling property and the like. The solvent drying (evaporation) conditions vary depending on the type, amount, and the like of the solvent in the solution, but may be usually dried at room temperature to 200 ° C. for about 10 seconds to 10 minutes.

  When the fluorine-containing graft copolymer of the present invention is blended in the coating liquid, a curable monomer component, a photopolymerization initiator, a solvent, and the like can be blended in the coating liquid.

  The curable monomer component is not particularly limited as long as it is a normal curable resin monomer component used in the coating liquid. For example, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tricyclodecane dimethylol diacrylate, bisphenol F EO-modified diacrylate, bisphenol A EO-modified diacrylate, isocyanuric acid EO-modified diacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, various urethane acrylate oligomers (Nippon Synthetic Chemical) Kogyo Kogyo Series, Negami Kogyo Art Resin Series, etc.). Not. These curable resin monomers may be used alone or in combination of two or more.

  The concentration of the fluorine-containing graft copolymer in the solution is not particularly limited, but is about 0.01 to 15 parts by weight, preferably 0.1 to 100 parts by weight of the curable resin monomer component contained in the coating liquid. About 10 parts by weight.

  The usage-amount of the curable resin monomer component in the coating liquid whole quantity is about 5-99.99 weight%, Preferably it is about 10-99.9 weight%. Moreover, the usage-amount of the fluorine-containing graft copolymer of this invention is about 0.0005-13 weight% in the coating liquid whole quantity, Preferably it is about 0.01-9 weight%.

  A conventionally well-known photoinitiator, a solvent, etc. can be mix | blended with a coating liquid as needed. Examples of the photopolymerization initiator include 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, and 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, benzophenone, and the like can be used. These photopolymerization initiators may be used alone or in combination of two or more.

  When using a photoinitiator and / or a solvent, the usage-amount of the curable resin monomer component in the coating liquid whole quantity is about 5 to 80 weight%, Preferably it is about 10 to 70 weight%. Moreover, the usage-amount of the fluorine-containing surface modifier of this invention is about 0.0005-13 weight% in the coating liquid whole quantity, Preferably it is about 0.01-9 weight%.

  When using a photopolymerization initiator, the amount of the photopolymerization initiator used is usually about 1 to 20 parts by weight, preferably about 2 to 15 parts by weight with respect to 100 parts by weight of the curable resin monomer component. . Solvents include alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xylene; ethers such as diethyl ether , Alkylene glycol monoethers such as diethylene glycol monoethyl ether, alkylene glycol diethers such as diethylene glycol diethyl ether, tetrahydrofuran, and 1,4-dioxane. These solvents may be used alone or in combination of two or more at any ratio.

  When the solvent is used, the amount of the solvent used is usually about 10 to 1900 parts by weight, preferably about 15 to 900 parts by weight with respect to 100 parts by weight of the curable resin monomer component.

  The coating method is not particularly limited, and a conventionally known coating method can be employed. For example, a bar coater or the like may be used. As an effect method, a method of curing by energy such as ultraviolet rays and heat can be adopted.

  The contents of the present invention will be described by the following examples, but the contents of the present invention are not intended to be limited to the examples.

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 2 shows the ¹ H-NMR data of the resulting fluorinated acrylate (6).

(In the formula, Rf is the following general formula (4) or (5).)

Synthesis example 2
In a three-necked flask (300 mL) equipped with a condenser tube, 51.2 g (0.1 mol) of NOF's Blemmer AE-400 [HO (CH ₂ CH ₂ O) ₁₀ C (═O) CH═CH ₂ ] 256 g of ethyl acetate, 0.82 g (5 mmol) of 2,2′-azobisisobutyronitrile and 0.3 g (2 mmol) of lauryl mercaptan were added. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After purging with nitrogen, the reaction solution was heated to 80 ° C. while stirring the reaction vessel 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 acrylate in ¹ H-NMR. The weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). Table 3 shows the measurement results.

Synthesis example 3
In a three-necked flask equipped with a cooling tube (200 mL), manufactured by NOF Corporation Blemmer _{AME-400 [CH 3 O (} CH 2 CH 2 O) 9 C (= O) CH = CH 2] 48.2g (0. 1 mol), 241 g of ethyl acetate, 0.82 g (5 mmol) of 2,2′-azobisisobutyronitrile and 0.2 g (1 mmol) of lauryl mercaptan were added. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After purging with nitrogen, the reaction solution was heated to 80 ° C. while stirring the reaction vessel 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 acrylate in ¹ H-NMR. The weight average molecular weight of the obtained 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, 21.7 g (0.045 mol) of Bremer AME-400 [CH ₃ O (CH ₂ CH ₂ O) ₉ C (═O) CH═CH ₂ ] manufactured by NOF Corporation ), 0.7 g (0.005 mol) of glycidyl methacrylate manufactured by Tokyo Chemical Industry Co., Ltd., 95 g of ethyl acetate, 0.42 g (5 mmol) of 2,2′-azobisisobutyronitrile, and 0.6 g (3 mmol) of lauryl mercaptan. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After purging with nitrogen, the reaction solution was heated to 80 ° C. while stirring the reaction vessel 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 acrylate in ¹ H-NMR. The weight average molecular weight of the fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). Table 3 shows the measurement results.

Example 1
In a three-necked flask (100 mL) equipped with a condenser tube, 25.5 g of the polymer synthesized in Synthesis Example 2 adjusted to 20% by mass with ethyl acetate and 0.06 g of benzoyl peroxide were placed. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After nitrogen substitution, the reaction vessel was heated to 80 ° C. while stirring the reaction vessel, and 9.5 g of fluorine-containing methacrylate synthesized in Synthesis Example 1 and adjusted to 20% by mass with ethyl acetate was added dropwise over 1 hour. After the dropping, stirring was continued at 80 ° C. for 5 hours to obtain a graft copolymer. The weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). The measurement results are shown in Table 4.

  The obtained fluorine-containing graft copolymer was adjusted to 50% by mass with ethyl acetate, 0.2 parts by weight of this, and pentaerythritol tri / tetraacrylate (manufactured by Nichia Gosei Co., Ltd., trade name: m-) as a curable resin monomer. 305) 20 parts by weight, 0.8 parts by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Ciba Specialty Chemicals, trade name: Irgacure 184) as a photopolymerization initiator, and 79 of methyl ethyl ketone (MEK) as a solvent Part by weight was mixed to prepare a coating solution. 15 mL of the prepared coating solution was placed in a 30 mL screw bottle, and the foaming property of the coating solution was confirmed by shaking up and down 120 times at a rate of twice per second. In addition, the coating solution was No. Spread it on a polyester film with a 20 bar coater, put it in a drier set at 60 ° C. for 2 minutes, volatilize the solvent, and then irradiate with UV to obtain a cured film. Water / oil repellency was evaluated. The measurement results are shown in Table 4.

Example 2
In a three-necked flask (100 mL) equipped with a condenser tube, 28.6 g of the polymer synthesized in Synthesis Example 2 adjusted to 20% by mass with ethyl acetate and 0.05 g of benzoyl peroxide were placed. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After nitrogen substitution, the reaction vessel was heated to 80 ° C. while stirring the reaction vessel, and 6.4 g of fluorine-containing methacrylate adjusted to 20% by mass with ethyl acetate synthesized in Synthesis Example 1 was added dropwise over 1 hour. After the dropping, stirring was continued at 80 ° C. for 5 hours to obtain a graft copolymer. The weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). The measurement results are shown in Table 4. Moreover, the coating liquid which mix | blended the obtained fluorine-containing copolymer was produced like Example 1, and surface smoothness, water repellency, oil repellency, and foaming property were evaluated similarly. The measurement results are shown in Table 4.

Example 3
In a three-necked flask (100 mL) equipped with a condenser tube, 35.1 g of the polymer synthesized in Synthesis Example 2 adjusted to 20% by mass with ethyl acetate and 0.02 g of benzoyl peroxide were placed. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After nitrogen substitution, the reaction vessel was heated to 80 ° C. while stirring the reaction vessel, and 4.9 g of fluorine-containing methacrylate synthesized in Synthesis Example 1 and adjusted to 20% by mass with ethyl acetate was added dropwise over 1 hour. After the dropping, stirring was continued at 80 ° C. for 5 hours to obtain a graft copolymer. The weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). The measurement results are shown in Table 4. Moreover, the coating liquid which mix | blended the obtained fluorine-containing copolymer was produced like Example 1, and surface smoothness, water repellency, and oil repellency were evaluated similarly. The measurement results are shown in Table 4.

Example 4
In a three-necked flask (100 mL) equipped with a condenser, 30.0 g of the polymer synthesized in Synthesis Example 3 adjusted to 20% by mass with ethyl acetate and 0.05 g of benzoyl peroxide were placed. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After nitrogen substitution, the reaction vessel was heated to 80 ° C. while stirring the reaction vessel, and 11.9 g of fluorine-containing methacrylate adjusted to 20% by mass with ethyl acetate synthesized in Synthesis Example 1 was added dropwise over 1 hour. After the dropping, stirring was continued at 80 ° C. for 5 hours to obtain a graft copolymer. The weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). The measurement results are shown in Table 4. Moreover, the coating liquid which mix | blended the obtained fluorine-containing copolymer was produced like Example 1, and surface smoothness, water repellency, oil repellency, and foaming property were evaluated similarly. The measurement results are shown in Table 4.

Example 5
In a three-necked flask (100 mL) equipped with a condenser tube, 35.1 g of the polymer synthesized in Synthesis Example 3 adjusted to 20% by mass with ethyl acetate and 0.05 g of benzoyl peroxide were placed. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After nitrogen substitution, the reaction vessel was heated to 80 ° C. while stirring the reaction vessel, and 11.9 g of the fluorine-containing methacrylate (20% by mass ethyl acetate solution) synthesized in Synthesis Example 1 was added dropwise over 1 hour. After the dropping, stirring was continued at 80 ° C. for 5 hours to obtain a graft copolymer. The weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). The measurement results are shown in Table 4. Moreover, the coating liquid which mix | blended the obtained fluorine-containing copolymer was produced like Example 1, and surface smoothness, water repellency, oil repellency, and foaming property were evaluated similarly. The measurement results are shown in Table 4.

Example 6
In a three-necked flask (100 mL) equipped with a condenser, 20.0 g of the polymer synthesized in Synthesis Example 4 adjusted to 20% by mass with ethyl acetate and 0.02 g of benzoyl peroxide were placed. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After nitrogen substitution, the reaction vessel was heated to 80 ° C. while stirring the reaction vessel, and 5.6 g of fluorine-containing methacrylate synthesized in Synthesis Example 1 and adjusted to 20% by mass with ethyl acetate was added dropwise over 1 hour. After the dropping, stirring was continued at 80 ° C. for 5 hours to obtain a graft copolymer. The weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). The measurement results are shown in Table 4. Moreover, the coating liquid which mix | blended the obtained fluorine-containing copolymer was produced like Example 1, and surface smoothness, water repellency, oil repellency, and foaming property were evaluated similarly. The measurement results are shown in Table 4.

Comparative Example 1
In a three-necked flask (200 mL) equipped with a condenser tube, 3.7 g of the fluorinated acrylate (6) synthesized in Synthesis Example 1, Bremer AE-400 [HO (CH ₂ CH ₂ O) ₁₀ C manufactured by NOF CORPORATION (═O) CH═CH ₂ ] 26.3 g, ethyl acetate 45 g, 2,2′-azobisisobutyronitrile 0.30 g, and lauryl mercaptan 1.22 g were added. Nitrogen gas was introduced into the reaction vessel, and the inside of the reaction vessel was replaced with nitrogen. After purging with nitrogen, the reaction solution was heated to 80 ° C. while stirring the reaction vessel to initiate 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 weight average molecular weight of the obtained fluorine-containing oligomer was confirmed using GPC (gel filtration chromatography). Table 4 shows the measurement results. Moreover, the coating liquid which mix | blended the obtained fluorine-containing copolymer was produced like Example 1, and surface smoothness, water repellency, oil repellency, and foaming property were evaluated similarly. The measurement results are shown in Table 4.

Evaluation (1) Surface smoothness
The surface of the effect film after UV irradiation was visually observed.
Evaluation criteria: No streak, repelling, etc. ○
There are streaks, repellents, etc. ×

(2) Water and oil repellency The contact angles of water and hexadecane on the cured film surfaces prepared in Examples and Comparative Examples were measured with a contact angle measuring device (DropMaster 700 manufactured by Kyowa Interface Chemical Co., Ltd.). The contact angle with water indicates the degree of water repellency, and the contact angle with hexadecane indicates the degree of oil repellency.

(3) Static surface tension After adjusting a 0.1% by mass solution of propylene glycol monomethyl ether acetate of the fluorinated copolymer synthesized in Examples 1-3 and Comparative Examples 1-2, a surface tension meter (Kyowa Interface) Scientific, SURFACE TENSIONMETER CBVP-Z) was measured at 22.degree. C. to 28.degree. C. by the Wilhelmy method. The measurement results are shown in Table 5.

  From Table 4 and Table 5, by using the fluorine-containing graft copolymer of the present invention, it is excellent in the ability to reduce the surface tension even with a smaller fluorine monomer ratio than the random copolymer, and the smoothness of the coating surface. It was found that application and water / oil repellency can be provided. Further, the fluorine-containing graft copolymer of the present invention has a lower foaming property than a random copolymer, and can be applied to uses where foaming is severely restricted.

  The fluorine-containing graft copolymer is useful as a surface modifier used in the fields of resins, engineering materials, paints, and the like, and is useful as a compound that can impart smoothness and water / oil repellency to the substrate surface. is there.

Claims (8)

A fluorine-containing graft copolymer comprising a (meth) acrylic acid ester represented by the following monomer (1) and at least one of the monomer (2) and the monomer (3) , -Contains a structural unit consisting of a fluorine-containing monomer represented by the following monomer (1) ,
A graft copolymer obtained by graft polymerizing the fluorine-containing monomer represented by the monomer (1) on a trunk polymer obtained by polymerizing at least one of the monomer (2) and the monomer (3) ; A fluorine-containing surface conditioner comprising:
[ Wherein , R f is a group represented by the following formula (4) or (5). R ¹ is a divalent linking group having 1 to 50 carbon atoms (this linking group optionally has a halogen atom, an ether bond, an ester bond, an amide bond or an aryl moiety).
R ³ is an organic group having 1 to 50 carbon atoms (the organic group may optionally have a halogen atom, an ether bond, an ester bond, an amide bond or an aryl moiety).
R ⁵ is a divalent linking group having 1 to 100 carbon atoms (the linking group may optionally have a halogen atom, an ether bond, an ester bond, an amide bond or an aryl moiety).
R ² , R ⁴ and R ⁶ are each independently H or a methyl group. ]
The fluorine-containing graft copolymer contains monomer (2) and monomer (3) as structural units, and is added to a trunk polymer obtained by copolymerization of monomer (2) and monomer (3). 2. The fluorine-containing surface conditioner according to claim 1, comprising a graft copolymer obtained by graft polymerization of a fluorine-containing monomer represented by the monomer (1).   The fluorine-containing surface conditioner according to claim 1 or 2, wherein the weight average molecular weight of the trunk polymer in the fluorine-containing graft copolymer is 2,000 to 50,000.   4. The fluorine-containing surface conditioner according to claim 1, wherein the fluorine-containing graft copolymer has a weight average molecular weight of 2,000 to 100,000.   In the fluorine-containing graft copolymer, the weight ratio of the total amount of monomer (1), monomer (2) and monomer (3) is monomer (1): monomer (2 ) And monomer (3) = 1: 99 to 55:45. The fluorine-containing surface conditioner according to claim 1, 2, 3, or 4. In the monomer (1), R ¹ is a divalent linking group having 2 to 30 carbon atoms (this linking group may optionally have an ether bond, an ester bond, an amide bond or an aryl moiety). The fluorine-containing surface conditioner according to claim 1, 2, 3, 4 or 5. The fluorine-containing graft copolymer contains the monomer (2) as a structural unit, and in the monomer (2), R ³ is an organic group having 1 to 30 carbon atoms (the organic group is an ether bond or ester if desired). The fluorine-containing surface conditioner according to claim 1, 2, 3, 4, 5, or 6, which may have a bond, an amide bond or an aryl moiety. The fluorine-containing graft copolymer contains the monomer (3) as a structural unit, and in the monomer (3), R ⁵ is a divalent linking group having 2 to 50 carbon atoms (the linking group is an ether if desired). The fluorine-containing surface conditioner according to claim 1, 2, 3, 4, 5, 6 or 7, which may have a bond, an ester bond, an amide bond or an aryl moiety.