Fluorine-containing surface modifier composition

Abstract

To provide a fluorine-containing surface modifier composition which is excellent in water repellency and oil repellency and is low in flammability and erosion resistance to a resin.SOLUTION: A fluorine-containing surface modifier composition contains a fluorine-containing polymer having a residue unit represented by the following formula (1) and a fluorine-based solvent. In the formula, Rf1 and Rf2 are fluorine-containing groups.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fluorine-containing surface modifier composition.

Background Art

[0002] Fluorine-containing compounds exhibit characteristic functions such as heat resistance, chemical resistance, water and oil repellency, low friction, and releasability based on the properties of carbon-fluorine bonds. Utilizing these properties, fluorine-containing compounds are used as surface modifiers that impart functions to various substrates, such as water and oil repellents, antifouling agents, release agents, and moisture-proof coating agents.

[0003] Hitherto, as a raw material for fluorine-containing surface modifiers, fluorine-containing polymers containing (meth)acrylate esters having a fluoroalkyl group as a polymerization unit have been used. In particular, fluorine-containing polymers containing a fluorine-containing (meth)acrylate ester having a perfluoroalkyl group with 8 or more carbon atoms as a polymerization unit are known to be excellent in dynamic water repellency and can effectively cause water droplets and the like adhering to the surface to slide off (see, for example, Non-Patent Document 1). However, compounds having a perfluoroalkyl group with 8 or more carbon atoms are regarded as having a problem of potentially having an adverse impact on the environment and living organisms, such as bioaccumulation. For this reason, substitution with a fluorine-containing polymer containing a fluorine-containing (meth)acrylate ester having a short-chain perfluoroalkyl group with 6 or less carbon atoms, which is considered to have low bioaccumulation, has been studied. However, it is known that surface modifiers composed of fluorine-containing polymers having a short-chain perfluoroalkyl group have reduced functions such as water and oil repellency compared to fluorine-containing polymers having a perfluoroalkyl group with 8 or more carbon atoms.

[0004] Patent Document 1 discloses a surface modifier containing a fluorine-containing (meth)acrylate polymer having an unsaturated bond in the side chain. However, since a non-fluorine-based organic solvent is used as the solvent, there are problems such as flammability and erosion to resin substrates, and further improvement has been demanded.

Prior Art Documents

Patent Document

[0005]

Patent Document 1

Non-Patent Document

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] An object of the present invention is to provide a fluorine-containing surface modifier composition that is excellent in water and oil repellency, has low flammability and low corrosiveness to resins, using a fluorine-containing polymer composed of a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventors have found that a composition containing a fluorine-containing polymer composed of a structural unit based on a fluorine-containing (meth)acrylate having an unsaturated bond in the side chain and a fluorine-based solvent having low flammability and low corrosiveness to resins exhibits excellent water and oil repellency, and thus have completed the present invention.

[0009] That is, the present invention relates to the following. [1] A fluorine-containing surface modifier composition comprising a fluorine-containing polymer having a residue unit represented by the following general formula (1) and a fluorine-based solvent.

Chemical Formula

[0010] Hereinafter, the present invention will be described in detail. In the fluorine-containing polymer having a residue unit represented by the general formula (1) of the present invention, Rf 1 is a perfluoroalkyl group having 1 to 6 carbon atoms. Among them, a linear perfluoroalkyl group having 1 to 6 carbon atoms is preferable, a linear perfluoroalkyl group having 4 to 6 carbon atoms is more preferable, and a linear perfluoroalkyl group having 6 carbon atoms is particularly preferable. In the fluorine-containing polymer having a residue unit represented by the general formula (1) of the present invention, Rf 2 is a perfluoroalkylene group having 1 to 6 carbon atoms. Among them, a linear perfluoroalkylene group having 1 to 6 carbon atoms is preferable, a linear perfluoroalkylene group having 4 to 6 carbon atoms is more preferable, and a linear perfluoroalkylene group having 6 carbon atoms is particularly preferable. In the general formula (1), Rf 1 -CH=CH-Rf 2 - The specific structures of the part include C2F5-CH=CH-C4F8-, C2F5-CH=CH-C6F 12 -, C4F9-CH=CH-C4F8-, C4F9-CH=CH-C6F 12 , C6F 13 -CH=CH-C4F8-, C6F 13 -CH=CH-C6F 12 - and the like, but are not limited thereto.

[0011] In the fluorine-containing polymer having a residue unit represented by the general formula (1) of the present invention, n is an integer of 1 to 4. Among them, n is preferably 2 to 3, and particularly preferably 2. In the fluorine-containing polymer having a residue unit represented by the general formula (1) of the present invention, R is a hydrogen atom or a methyl group.

[0012] As one of the preferred embodiments of the present invention, the fluorine-containing polymer is obtained by polymerizing a fluorine-containing (meth)acrylate represented by the general formula (2) (hereinafter, when copolymerized with other monomers using the fluorine-containing (meth)acrylate, it may be referred to as "monomer A"). Here, when polymerizing the fluorine-containing (meth)acrylate represented by the general formula (2) alone, it may be referred to as homopolymerization. In this embodiment, the polymerization method is not particularly limited, and for example, solution polymerization using a solvent can be carried out.

[0013] In this embodiment, the solvent used in solution polymerization is not particularly limited. Specifically, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n-hexane, n-heptane, mineral spirit, and cyclohexane; halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and orthodichlorobenzene; ester or ester-ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, and benzyl alcohol; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methyl-2-pyrrolidone; and fluorine solvents such as trifluoromethylbenzene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, pentafluorobutane, decafluoropentane, perfluorohexane, perfluorocyclohexane, perfluorodecalin, hexafluorobenzene, and hydrofluoroether can be mentioned. These solvents may be used alone or in combination of two or more. In this embodiment, the amount of the solvent used in solution polymerization is not particularly limited. However, it is preferably 1 to 200 times by weight, more preferably 2 to 100 times by weight, based on the monomer A in the polymerization reaction.

[0014] In this embodiment, for example, by using a polymerization initiator, a polymerization reaction can be advanced. The polymerization initiator is not particularly limited, and examples thereof include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2-(carbamoylazo)isobutyronitrile, peroxides such as benzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxypivalate, lauryl peroxide, and persulfates such as potassium persulfate and ammonium persulfate. These polymerization initiators may be used alone or in combination of two or more. In this embodiment, the amount of the polymerization initiator used is not particularly limited, but it is preferably 0.001% by weight to 50% by weight, more preferably 0.005% by weight to 20% by weight, and particularly preferably 0.01% by weight to 10% by weight based on the monomer A involved in the polymerization reaction.

[0015] In this embodiment, the polymerization reaction is carried out under normal pressure, under pressure in a sealed state, or under reduced pressure, and it is preferably carried out under normal pressure because of the simplicity of the apparatus and operation. Also, it is preferably carried out in an inert gas atmosphere such as nitrogen. The temperature of the polymerization reaction is preferably 40°C to 150°C, more preferably 40°C to 100°C. The polymerization reaction time is preferably in the range of 1 hour to 48 hours, and more preferably in the range of 1 hour to 24 hours. These reaction temperature and reaction time conditions may be appropriately adjusted according to the type and amount of the monomer A and the type and amount of the polymerization initiator.

[0016] In this embodiment, after the completion of the polymerization reaction, the obtained fluorine-containing polymer is recovered by any method, and post-treatment such as purification is carried out as necessary. As a method for recovering the polymer from the reaction solution, known methods such as concentration and reprecipitation can be used.

[0017] In this embodiment, the weight average molecular weight (hereinafter abbreviated as Mw) of the obtained fluorine-containing polymer is preferably from 1,000 to 1,000,000, more preferably from 10,000 to 500,000 in terms of polystyrene conversion by gel permeation chromatography (GPC).

[0018] As one of the preferred embodiments of the present invention, apart from monomer A which is a raw material of the above-mentioned fluorine-containing polymer, a monomer B which copolymerizes with or can copolymerize with monomer A is used for copolymerization to obtain a fluorine-containing polymer, and a fluorine-containing surface modifier composition containing at least this fluorine-containing polymer and a fluorine-based solvent can be mentioned. Here, monomer B which copolymerizes with or can copolymerize with monomer A may be any monomer as long as a fluorine-containing polymer can be formed. Further, the structure of the copolymerized fluorine-containing polymer has residue units derived from monomer A and monomer B. In addition, monomer B is not particularly limited as long as it copolymerizes with or can copolymerize with monomer A. Further, monomer B may be a specific single type, but may also be two or more types in addition to monomer A. In the present invention, monomer A which is a fluorine-containing (meth)acrylate represented by general formula (2) can be variously applied as the compound structure represented by general formula (2). Among them, the combination with monomer B which copolymerizes with or can copolymerize with monomer A can be adopted after appropriate consideration. Further, other copolymerization conditions can also be adopted after appropriate consideration.

[0019] Furthermore, when the fluorine-containing polymer is composed of monomer A and monomer B which copolymerizes with monomer A, as the blending ratio during the polymerization reaction of monomer A and monomer B, it is preferable that the weight ratio (A) / (B) of monomer A and monomer B is a weight ratio of 1:99 to 99.9:0.1, and a weight ratio of 10:90 to 99.9:0.1 is more preferable.

[0020] In this embodiment, monomer B is not particularly limited as long as it can copolymerize with or be copolymerizable with monomer A, but is preferably at least one selected from the group consisting of (meth)acrylic acid, esters of (meth)acrylic acid, styrenes, fatty acid vinyl esters, vinyl halides, vinylidene halides, fatty acid allyl esters, and acrylamides. Specifically, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate, behenyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 4-cyanophenyl (meth)acrylate, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate esters, styrene, α-methylstyrene, p-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, allyl heptanoate, allyl caprylate, allyl caproate, N-methylacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, etc. These monomers may be used alone or in combination of two or more.

[0021] In this embodiment, the polymerization method is not particularly limited, and for example, solution polymerization using a solvent can be carried out.

[0022] In this embodiment, the solvent used in solution polymerization is not particularly limited. Specifically, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbon solvents such as n - hexane, n - heptane, mineral spirit, and cyclohexane; halogen solvents such as methyl chloride, methyl bromide, methyl iodide, methylene dichloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, and orthodichlorobenzene; ester or ester - ether solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diethyl ether, tetrahydrofuran, 1,4 - dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di - n - butyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, n - propanol, isopropanol, n - butanol, isobutanol, tert - butanol, 2 - ethylhexyl alcohol, and benzyl alcohol; amide solvents such as N,N - dimethylformamide and N,N - dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N - methyl - 2 - pyrrolidone; fluorine solvents such as trifluoromethylbenzene, 1,3 - bis(trifluoromethyl)benzene, 1,4 - bis(trifluoromethyl)benzene, 1,1,1,2,2 - pentafluoro - 3,3 - dichloropropane, 1,1,2,2,3 - pentafluoro - 1,3 - dichloropropane, pentafluorobutane, decafluoropentane, perfluorohexane, perfluorocyclohexane, perfluorodecalin, hexafluorobenzene, and hydrofluoroether, etc. These solvents may be used alone or in combination of two or more. In this embodiment, the amount of the solvent used in solution polymerization is not particularly limited. However, it is preferably 1 to 200 times by weight, more preferably 2 to 100 times by weight, based on the total amount of monomer A and monomer B in the polymerization reaction.

[0023] In this embodiment, for example, by using a polymerization initiator, the polymerization reaction can be advanced. The polymerization initiator is not particularly limited. For example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2-(carbamoylazo)isobutyronitrile; peroxides such as benzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxypivalate, lauryl peroxide; persulfates such as potassium persulfate, ammonium persulfate, etc. can be mentioned. These polymerization initiators may be used alone or in combination of two or more. In this embodiment, the amount of the polymerization initiator used is not particularly limited, but is preferably 0.001% by weight to 50% by weight, more preferably 0.005% by weight to 20% by weight, and particularly preferably 0.01% by weight to 10% by weight based on the total amount of monomer A and monomer B involved in the polymerization reaction.

[0024] In this embodiment, the polymerization reaction is carried out under normal pressure, under pressure in a sealed state, or under reduced pressure. From the simplicity of the apparatus and operation, it is preferably carried out under normal pressure. Also, it is preferably carried out in an inert gas atmosphere such as nitrogen. The temperature of the polymerization reaction is preferably 40°C to 150°C, more preferably 40°C to 100°C. The polymerization reaction time is preferably in the range of 1 hour to 48 hours, and more preferably in the range of 1 hour to 24 hours. These reaction temperature and reaction time conditions may be appropriately adjusted according to the type and amount of monomer A, and the type and amount of the polymerization initiator.

[0025] In this embodiment, after the completion of the polymerization reaction, the obtained fluorine-containing polymer is recovered by an arbitrary method, and post-treatment such as purification is carried out as necessary. As a method for recovering the polymer from the reaction solution, known methods such as concentration, reprecipitation, etc. can be used.

[0026] In this embodiment, the weight average molecular weight (hereinafter abbreviated as Mw) of the obtained fluorine-containing polymer is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000 in terms of polystyrene conversion by gel permeation chromatography (GPC).

[0027] The fluorine-containing polymer of the present invention can be dissolved in a fluorine-based solvent and used as a fluorine-containing surface modifier composition containing the fluorine-containing polymer and the fluorine-based solvent. By making it into a solution composition, it can be made into a form capable of treating a substrate by coating, dipping, etc. The use of the surface modifier composition of the present invention is not particularly limited, but it can be used, for example, as a coating agent, a water / oil repellent, a rust preventive, an antifouling agent, a water resistance agent, a release agent, a mold release agent, an oil barrier agent, a flux creep prevention agent, etc.

[0028] In the fluorine-containing surface modifier composition of the present invention, the fluorine-based solvent contains at least one selected from the group consisting of hydrofluoroethers, hydrofluorocarbons, perfluorocarbons, hydrochlorofluorocarbons, and chlorofluorocarbons. Specifically, for example, methyl nonafluorobutyl ether (HFE7100), ethyl nonafluorobutyl ether (HFE7200), 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl) pentane (HFE7300), pentafluorobutane, decafluoropentane, perfluorohexane, perfluorocyclohexane, perfluorodecalin, hexafluorobenzene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,2,3,3-tetrachlorohexafluorobutane, etc. can be mentioned. Among them, methyl nonafluorobutyl ether (HFE7100), ethyl nonafluorobutyl ether (HFE7200), 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl) pentane (HFE7300), decafluoropentane, perfluorohexane, perfluorocyclohexane, perfluorodecalin, etc. are preferable from the viewpoint of having no flash point and being easy to handle. These solvents may be used alone or in combination of two or more. These solvents may be appropriately selected and used according to the purpose of use. By using a fluorine-based solvent, it is useful in that a fluorine-containing polymer can be uniformly dissolved and a composition having low flammability and low erodibility to the resin can be obtained. In the surface modifier composition of the present invention, it is preferable to contain 0.01 to 50% by weight of the fluorine-containing polymer, and more preferably 0.05% to 20% by weight, based on the total amount of the fluorine-containing polymer and the fluorine-based solvent.

[0029] The surface modifier composition of the present invention may be prepared by mixing the obtained fluorine-containing polymer and the above fluorinated solvent, or the fluorine-containing polymer solution obtained by solution polymerization using a fluorinated solvent may be used as a surface modifier as it is, or it may be prepared by further diluting the fluorine-containing polymer solution obtained by solution polymerization using a fluorinated solvent with a solvent.

[0030] The substrate to be treated with the surface modifier composition of the present invention is not particularly limited, and examples include metals, plastics, ceramics, etc. In particular, when treating electronic components such as printed circuit boards, the surface modifier composition of the present invention is useful because of its low erosiveness.

[0031] The treatment of the substrate with the surface modifier composition of the present invention can be carried out by any commonly used method such as brush coating, coating by wiping or using a wiper, dipping, spraying by atomization, spraying with a spray gun, aerosol spraying, etc.

Advantages of the Invention

[0032] By using the fluorine-containing surface modifier composition of the present invention, excellent water and oil repellency, etc. can be imparted to the substrate surface. Furthermore, the composition is composed of a perfluoroalkyl group having 6 or less carbon atoms, which is said to have low bioaccumulation properties, and has low flammability and low erosiveness to resins.

Examples

[0033] Examples of the present invention are shown below, but the present invention is not limited by these examples. In the analysis, the following equipment was used. <nmr> Apparatus: Bruker AVANCE II 400 Internal standards: Tetramethylsilane, Trifluoromethylbenzene Solvent: Acetone-d6 <gpc> Equipment: HLC-8320GPC manufactured by Tosoh Column: TSKgel G4000H / G3000H / G2500H / G2000H Eluent: hexafluoroisopropanol or tetrahydrofuran Flow rate: 0.3 mL / min or 1 mL / min <dsc> Apparatus: DSC Q2000 manufactured by TA Instruments Scanning rate: 10 °C / min

[0034] <Measurement of Contact Angle> For the sample to be measured (the polymer shown below), the static contact angles of pure water and diiodomethane, and the dynamic contact angle of pure water by the spreading / contracting method were measured. Specifically, a predetermined amount of the polymer, which is the sample to be measured, was dissolved in a fluorine-based solvent, and then filtered through a syringe filter with a pore size of 0.45 μm to prepare a polymer solution with a predetermined concentration. This polymer solution was spin-coated onto a 2-inch diameter silicon wafer to form a film. An active manual spin coater ACT-300AII was used for spin coating, and a contact angle meter DMs-401 manufactured by Kyowa Interface Science was used for contact angle measurement.

[0035] Here, for the static contact angle, it is measured for the purpose of measurement such as quantification of wettability. When a liquid droplet is brought into contact with the solid surface and adheres, the angle formed with the sample surface is defined as the contact angle θ. In the present invention, the θ / 2 method was used for analysis. The larger the static contact angle, the better the water and oil repellency. Also, for the dynamic contact angle, it is measured for the purpose of quantification of liquid removability. The contact angle when the wetting spreads (expansion) is defined as the (dynamic) advancing angle, and the contact angle when it contracts is defined as the (dynamic) receding angle. In the present invention, the spreading / contracting method was used, and the true circle fitting method was used for analysis. The smaller the contact angle hysteresis, which is the difference between the advancing contact angle and the receding contact angle obtained from the dynamic contact angle measurement, the better the dynamic water repellency.

[0036] Example 1 Synthesis of Polymer 1

Chemical Formula

[0037] Example 2 Synthesis of Polymer 2 [Chemical formula] In Example 1, 4.09 g of Polymer 2 was obtained as a white solid by the same operation except that 5.00 g of compound (4) (manufactured by Tosoh Finechem) was used instead of compound (3). The yield was 82%. The number average molecular weight Mn measured by GPC in terms of PMMA of the obtained target product was 13,000, and the dispersity Mw / Mn was 2.7. When DSC measurement was performed, the melting temperature was 42.7 °C.

[0038] Comparative Example 1 Synthesis of Polymer 3 In Example 1, 3.50 g of Polymer 2 was obtained as a colorless solid by the same operation except that 5.00 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-n-octyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of compound (3). The yield was 70%. The number average molecular weight Mn measured by GPC in terms of PMMA of the obtained target product was 6,400, and the dispersity Mw / Mn was 1.5. When DSC measurement was performed, the glass transition temperature was 24.8 °C.

[0039] Comparative Example 2 Synthesis of Polymer 4 In Example 1, except that 5.00 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-n-octyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of compound (3), 4.00 g of Polymer 2 was obtained as a colorless viscous substance by the same operation. The yield was 80%. The number average molecular weight Mn measured by GPC in terms of polystyrene of the obtained target product was 5,500, and the dispersity Mw / Mn was 1.4. When DSC measurement was performed, the glass transition temperature was -16.1 °C.

[0040] Example 3 20 mg of Polymer 1 obtained in Example 1 was dissolved in 1.98 g of decafluoropentane (manufactured by Mitsui Chemicals Fluoro Products), and then filtered through a syringe filter with a pore size of 0.45 μm to obtain a 1.0 wt% polymer solution, and a surface modifier composition was prepared. This composition was spin-coated (slope for 5 seconds, then 2,000 rpm for 10 seconds, and further slope for 5 seconds) on a 2-inch diameter silicon wafer to form a film. For the obtained thin film, the static contact angles of pure water and diiodomethane (droplet volume 2 μL) and the dynamic contact angle of pure water by the expansion / contraction method were measured by the method described above.

[0041] Example 4 In Example 3, the same measurement was performed using Polymer 2 instead of Polymer 1.

[0042] Comparative Example 3 In Example 3, the same measurement was performed using Polymer 3 instead of Polymer 1.

[0043] Comparative Example 4 In Example 3, the same measurement was performed using Polymer 4 instead of Polymer 1.

[0044] The results obtained above are shown in Table 1.

[0045] [Table 1]

[0046] From the results in Table 1, it can be seen that the thin films formed by the fluorine-containing polymer and the surface modifier containing a fluorine-based solvent of the present invention shown in Examples 3 and 4 are as follows when compared with the thin films formed by the surface modifier containing a conventional fluorine-containing polymer having a perfluoroalkyl group with 6 or less carbon atoms shown in Comparative Examples 3 and 4. From the measurement results of the static contact angle with respect to pure water, the results of Examples 3 and 4 are higher than those of Comparative Examples 3 and 4, indicating excellent water repellency. From the measurement of the static contact angle with respect to diiodomethane, the results of Examples 3 and 4 are higher than those of Comparative Examples 3 and 4, indicating excellent oil repellency. From the measurement results of the dynamic contact angle with respect to pure water, although the results of Examples 3 and 4 for the advancing contact angle are generally the same as those of Comparative Examples 3 and 4, the results of Examples 3 and 4 for the receding contact angle are higher than those of Comparative Examples 3 and 4, and the contact angle hysteresis is small, indicating excellent water droplet removability.

[0047] Example 5 Synthesis of Polymer 5 0.80 g of compound (3) (manufactured by Tosoh Finechem), 0.20 g of 2-ethylhexyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4.00 g of 2-butanone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 10.0 mg of t-butyl peroxyoctoate (manufactured by NOF Corporation) were charged into a 10 mL test tube. After nitrogen substitution, the mixture was stirred at 75 °C for 12 hours. After completion of the reaction, the supernatant of the reaction solution separated into two layers was decanted and then dried under vacuum to obtain 0.62 g of Polymer 5 as a colorless solid. The yield was 62%. The number average molecular weight Mn measured by GPC in terms of polystyrene conversion of the obtained target product was 16,000, and the dispersity Mw / Mn was 1.3. 1 The copolymerization ratio measured by 1H NMR showed that the residue unit consisting of 2-ethylhexyl methacrylate in the copolymer was 21% (weight conversion, the same hereinafter).

[0048] Example 6 Synthesis of Polymer 6 In Example 5, 0.20 g of dodecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2-ethylhexyl methacrylate, and 0.69 g of Polymer 6 was obtained as a colorless solid in the same manner. The yield was 69%. The number average molecular weight Mn measured by GPC in terms of polystyrene of the obtained target product was 11,000, and the dispersity Mw / Mn was 1.5. 1 The copolymerization ratio measured by 1H NMR showed that the residue unit consisting of dodecyl methacrylate in the copolymer was 24%.

[0049] Comparative Example 5 Synthesis of Polymer 7 In Example 5, 0.80 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-n-octyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of Compound (3), and 0.76 g of Polymer 7 was obtained as a colorless solid in the same manner. The yield was 76%. The number average molecular weight Mn measured by GPC in terms of polystyrene of the obtained target product was 11,000, and the dispersity Mw / Mn was 1.8. 1 The copolymerization ratio measured by 1H NMR showed that the residue unit consisting of 2-ethylhexyl methacrylate in the copolymer was 18%.

[0050] Comparative Example 6 Synthesis of Polymer 8 In Example 6, 0.80 g of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-n-octyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of Compound (3), and 0.77 g of Polymer 8 was obtained as a colorless solid in the same manner. The yield was 77%. The number average molecular weight Mn measured by GPC in terms of polystyrene of the obtained target product was 16,000, and the dispersity Mw / Mn was 1.6. 1 The copolymerization ratio measured by 1H NMR showed that the residue unit consisting of dodecyl methacrylate in the copolymer was 19%.

[0051] Example 7 After dissolving 20 mg of Polymer 5 obtained in Example 5 in 1.98 g of ethyl nonafluorobutyl ether (manufactured by 3M), the solution was filtered through a syringe filter with a pore size of 0.45 μm to obtain a 1.0 wt% polymer solution, and a surface modifier composition was prepared. This composition was spin-coated (slope for 5 seconds, then 2,000 rpm for 10 seconds, and further slope for 5 seconds) onto a silicon wafer with a diameter of 2 inches to form a film. For the obtained thin film, the static contact angles of pure water and diiodomethane (droplet volume: 2 μL) were measured by the method described above. Example 8 In Example 7, the same measurement was performed using Polymer 6 instead of Polymer 5.

[0052] Comparative Example 7 In Example 7, the same measurement was performed using Polymer 7 instead of Polymer 5.

[0053] Comparative Example 8 In Example 7, the same measurement was performed using Polymer 8 instead of Polymer 5.

Table 2

[0054] From the results in Table 2, it can be seen that the thin films formed by the surface modifier containing the fluorinated polymer and the fluorinated solvent of the present invention shown in Examples 7 and 8 are as follows compared with the thin films formed by the surface modifier containing the conventional fluorinated polymer having a perfluoroalkyl group with 6 or less carbon atoms shown in Comparative Examples 7 and 8. Comparing Example 7 with Comparative Example 7, both are composed of 2-ethylhexyl methacrylate as Monomer B. In this case, regarding the measurement results of the static contact angle with respect to pure water, the result of Example 7 is higher than that of Comparative Example 7, indicating excellent water repellency, and the measurement results of the static contact angle with respect to diiodomethane are about the same for both. From this, it can be seen that Polymer 5 composed of Compound (3) as Monomer A is more excellent in water repellency, and the composition of the present invention is excellent in water repellency. When Example 8 is compared with Comparative Example 8, both are composed of dodecyl methacrylate as Monomer B. In this case, regarding the measurement results of the static contact angle with respect to pure water, the result of Example 8 is higher than that of Comparative Example 8, indicating excellent water repellency. In the measurement results of the static contact angle with respect to diiodomethane, the two are comparable. From this, it can be seen that the polymer 6 composed of the monomer A from the compound (3) is more excellent in water repellency, and it can be understood that the composition of the present invention is excellent in water repellency.

[0055] From the above results, it can be seen that the thin film formed by the surface modifier containing the fluoropolymer and the fluorinated solvent of the present invention exhibits excellent water and oil repellency compared to the thin film formed by the conventional surface modifier containing a fluoropolymer having a perfluoroalkyl group with 6 or less carbon atoms.

Industrial Applicability

[0056] By using the composition containing the fluoropolymer and the fluorinated solvent of the present invention, a fluorine-containing surface modifier composition excellent in water and oil repellency and having low flammability and low erosion to resins can be provided, which is industrially useful.< / dsc> < / gpc> < / nmr>

Claims

1. A fluorine-containing surface modifier composition comprising a fluorine-containing polymer having a residue unit represented by the following general formula (1) and at least one fluorine-based solvent selected from the group consisting of hydrofluoroethers, hydrofluorocarbons, and perfluorocarbons. 【Chemical Formula 5】 (In formula (1), Rf １ is a perfluoroalkyl group having 1 to 6 carbon atoms, Rf ２ is a perfluoroalkylene group having 1 to 6 carbon atoms, n is an integer of 1 to 4, and R is a hydrogen atom or a methyl group.)

2. The fluorine-containing surface modifier composition according to claim 1, wherein the fluorine-containing polymer is obtained by polymerizing a fluorine-containing (meth)acrylate represented by the following general formula (2). 【Chemical Formula 6】 (In formula (1), Rf １ is a perfluoroalkyl group having 1 to 6 carbon atoms, and Rf ２ is a perfluoroalkylene group having 1 to 6 carbon atoms, n is an integer of 1 to 4, and R is a hydrogen atom or a methyl group.)

3. The fluorine-containing surface modifier composition according to claim 1, wherein the fluorine-containing polymer is composed of monomer A and monomer B copolymerizable with monomer A, and the weight ratio (A) / (B) of monomer A to monomer B is copolymerized at a weight ratio of 1:99 to 99.9:0.

1.

4. The fluorine-containing surface modifier composition according to claim 1 or claim 3, wherein monomer B is at least one selected from the group consisting of (meth)acrylic acid, esters of (meth)acrylic acid, styrenes, fatty acid vinyl esters, vinyl halides, vinylidene halides, fatty acid allyl esters, and acrylamides.

5. The fluorine-containing surface modifier composition according to any one of claims 1 to 4, comprising 0.01% by weight to 50% by weight of the fluorine-containing polymer based on the total amount of the fluorine-containing polymer and the fluorine-based solvent.

Images