JP2019189545A - Reactive fluorine-containing sulfonylimide and polymer thereof, and antistatic agent containing the same - Google Patents

Abstract

To provide a novel compound capable of preventing bleeding out from a resin, and having excellent antistatic action, and an antistatic agent containing the same.SOLUTION: There is provided a polymer having reactive fluorine-containing sulfonylimide represented by the following general formula (1) and a repeating unit based thereon. In the general formula (1), Rrepresents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkali metal ion or an onium cation, Rrepresents a methyl group or an ethyl group, Rfrepresents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms, Rfrepresents a linear or branched perfluoroalkylene group having 1 to 4 carbon atoms, X represents a connection group which is a bivalent organic group, and Arepresents an alkali metal ion or an onium cation.SELECTED DRAWING: None

Description

  The present invention relates to a reactive fluorine-containing sulfonylimide, a polymer thereof, and an antistatic agent containing the same.

  Since the resin generally has a high surface resistivity, it has a property of being easily charged with static electricity by a physical action such as friction. The static electricity charged on the resin may cause an electric shock to the electronic device and cause a malfunction such as malfunction or data corruption. In addition, the resin charged with static electricity is easy to adsorb dust and dust, and not only looks bad, but also contaminates the surrounding electronic devices, which may cause malfunctions and data corruption. . For this reason, an antistatic agent is added to the resin to reduce the surface resistivity of the resin product.

In Patent Document 1, as antistatic agents, dimethyldimethoxysilane, methyltrimethoxysilane, 1- (3-trimethoxysilylpropyl) -1,1,1-tributylphosphonium = bis (trifluoromethanesulfonyl) imide and A polysiloxane copolymer obtained by copolymerizing is disclosed. According to Example 12 of Patent Document 1, a silicone resin pressure-sensitive adhesive prepared by adding 48 mg of the polysiloxane copolymer to 4.0 g of a peroxide-curable silicone pressure-sensitive adhesive (solid content: 60%). The layer has a surface resistivity of 7.5 × 10 ¹¹ Ω / □ and is compared with a silicone resin pressure-sensitive adhesive layer (surface resistivity:> 10 ¹⁵ Ω / □) prepared without adding a polysiloxane copolymer. Has been reduced.

Japanese Patent No. 6179668

  By the way, with the recent refinement of electronic equipment, there is an increasing need to protect electronic equipment from electrical shock due to static electricity, contamination from dust, dust, etc., and various resins such as cases and protective films of electronic equipment. There is a demand for further improvement in antistatic performance of molded products.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel compound that can prevent bleed out from a resin and has an excellent antistatic action and an antistatic agent containing the same. There is.

As a result of intensive studies on the above problems, the inventor of the present invention has a reactive fluorine-containing sulfonylimide having a trialkoxysilyl group as a reactive functional group and an alkali metal ion or onium cation as a cation component, and a unit based thereon The present invention was completed by finding that adding a polymer containing a resin to a resin makes it possible to obtain a resin composition that hardly causes bleed out, has low surface resistivity, and is hardly charged with static electricity. I let you.
That is, the present invention has the following configuration.

[1] Reactive fluorine-containing sulfonylimide represented by the following general formula (1).

However, in the above general formula (1), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkali metal ion or an onium cation, and R ² represents a methyl group or an ethyl group. Rf ¹ represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms, and Rf ² represents a linear or branched perfluoroalkylene group having 1 to 4 carbon atoms. X represents a linking group which is a divalent organic group, and A ⁺ represents an alkali metal ion or an onium cation.

[2] The reactive fluorine-containing sulfonylimide according to [1], wherein Rf ² is a linear perfluoroalkylene group having 3 carbon atoms.

[3] The reactive fluorine-containing sulfonylimide according to [1] or [2], wherein X is a divalent organic group represented by the following general formula (2).

  However, in said general formula (2), * represents a joint with Si.

[4] The reactive fluorine-containing sulfonylimide according to any one of [1] to [3], wherein the A ⁺ is an alkali metal ion.

[5] An antistatic agent comprising the reactive fluorine-containing sulfonylimide according to any one of [1] to [4].

[6] A polymer having a repeating unit based on the reactive fluorine-containing sulfonylimide according to any one of [1] to [4].

[7] An antistatic agent comprising the polymer according to [6].

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the novel compound which can prevent the bleed out from resin, and has the outstanding antistatic effect, and the antistatic agent containing this.

  Hereinafter, the reactive fluorine-containing sulfonyl imide which is one Embodiment concerning this invention, its polymer, and the antistatic agent containing it are demonstrated in detail.

<Reactive fluorine-containing sulfonylimide>
The reactive fluorine-containing sulfonylimide of this embodiment is represented by the following general formula (1).

In the general formula (1), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkali metal ion, or an onium cation. Examples of alkali metal ions include lithium, sodium, and potassium. An onium cation is, for example, at least one organic compound formed by coordination of a cation-type atomic group to a compound containing an element having a lone pair such as nitrogen, sulfur, oxygen, phosphorus, selenium, tin, iodine, and antimony. If it is a cation which has group, it will not restrict | limit in particular. As the onium cation, ammonium cations, pyrrolidinium cations, imidazolium cations, pyridinium cations, sulfonium cations, and phosphonium cations can be used. Examples of ammonium cations include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, ethyltrimethylammonium cation, trimethylpropylammonium cation, trimethylisopropylammonium cation, butyltrimethylammonium cation, hexyltrimethylammonium cation, octyltrimethylammonium Cation, dodecyltrimethylammonium cation, vinyltrimethylammonium cation, allyltrimethylammonium cation, triethylmethylammonium cation, triethylpropylammonium cation, triethylmethoxymethylammonium cation, tributylethylammonium cation, diethyldi It can be exemplified chill ammonium cations, dimethyl dipropyl ammonium cation, hexamethonium cation, and the like. Examples of pyrrolidinium cations include N, N-dimethylpyrrolidinium cation, N, N-diethylpyrrolidinium cation, N, N-dipropylpyrrolidinium cation, N-ethyl-N-methylpyrrolidi Examples thereof include a nium cation, an N-methyl-N-propylpyrrolidinium cation, an N-butyl-N-methylpyrrolidinium cation, and an N-hexyl-N-methylpyrrolidinium cation. Examples of imidazolium cations include 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1,3-dipropylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1- Examples thereof include methyl-3-propylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-isopropyl-3-propylimidazolium cation, 1-tert-butyl-3-isopropylimidazolium cation, and the like. Examples of pyridinium cations include N-ethylpyridinium cation and N-butylpyridinium cation. Examples of sulfonium cations include trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, diethylmethylsulfonium cation, dimethylpropylsulfonium cation, and hexyldimethylsulfonium cation. Examples of phosphonium cations include tetramethylphosphonium cation, tetraethylphosphonium cation, tetrapropylphosphonium cation, tetrabutylphosphonium cation, tetraoctylphosphonium cation, tetraphenylphosphonium cation, ethyltrimethylphosphonium cation, triethylmethylphosphonium cation, hexyltrimethylphosphonium. A cation, a trimethyloctyl phosphonium cation, etc. can be mentioned.
R ¹ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

R ² represents a methyl group or an ethyl group.
Rf ¹ represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms.
Rf ² represents a straight-chain or branched perfluoro alkylene group having 1 to 4 carbon atoms. Rf ² is preferably a linear perfluoroalkylene group, particularly preferably a linear perfluoroalkylene group having 3 carbon atoms.

  X represents a linking group which is a divalent organic group. Examples of the divalent organic group include a divalent hydrocarbon group, an oxygen atom (ether bond), a sulfur atom (sulfide bond), a carbonyl group, an imino group, a sulfone group, and a combination thereof. The divalent hydrocarbon group preferably has 1 to 10 carbon atoms. The divalent hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The divalent hydrocarbon group may be a linear or branched chain hydrocarbon group, a cyclic hydrocarbon group, or a combination of these. Good. Examples of the chain hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group. Examples of the cyclic hydrocarbon group include a cycloalkylene group and a phenylene group. The divalent hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group and an alkoxy group having 1 to 6 carbon atoms. In the imino group, a hydrogen atom may be substituted with a linear or branched alkyl group having 1 to 10 carbon atoms.

Examples of the group in which a divalent organic group is combined include an oxyalkylene group (—O-alkylene group—), an iminoalkylene group (—NH-alkylene group—), an ester bond (—O—C (═O) — ), Amide bond (—C (═O) —NH—), sulfonamide bond (—S (═O) ₂ —NH—), urethane bond (—O—C (═O) —NH—), urea bond (-NH-C (= O) -NH-) and the group which combined these can be mentioned.

  X is preferably a divalent organic group represented by the following general formula (2).

  However, in said general formula (2), * represents a joint with Si.

A ⁺ represents an alkali metal ion or an onium cation. Examples of alkali metal ions and onium cations are the same as above. A ⁺ is preferably an alkali metal ion, particularly preferably a lithium ion.

Next, regarding the method for producing the reactive fluorine-containing sulfonylimide of the present embodiment, R ¹ is a methyl group, X is a divalent organic group represented by the general formula (2), and A ⁺ is Description will be made by taking a reactive fluorine-containing sulfonylimide which is a lithium ion as an example. This reactive fluorine-containing sulfonylimide can be produced by the reactions shown in the following reaction formulas 1ie to 4ie and 1e. In the following reaction formulas 1ie to 4ie and 1e, R ² , Rf ¹ and Rf ² are the same as those in the general formula (1).

First, as shown in Scheme 1ie below, perfluoro alkane sulfonyl difluoride and ^{_{(F-S (= O)}} 2 -Rf 2 -S (= O) 2 -F), perfluoroalkane sulfonamide potassium The intermediate (1ie) is synthesized by reacting with a salt (Rf ¹ —S (═O) ₂ —N ^— HK ⁺ ). This reaction can be performed, for example, in dehydrated acetonitrile (dry-CH ₃ CN) in the presence of potassium fluoride.

Next, as shown in the following reaction formula 2ie, the intermediate 1ie is reacted with methylamine in the presence of potassium fluoride, and the fluorine atom at the terminal of the intermediate 1ie is converted to a methylaminopotassium base (—N ⁻ Substitute CH ₃ K ⁺ ) to synthesize intermediate 2ie. This reaction can be performed, for example, in dehydrated tetrahydrofuran (dry-THF).

Next, as shown in the following reaction formula 3ie, the intermediate 2ie is reacted with 2-chloroethanol, and the methylamino potassium base potassium of the intermediate 2ie is replaced with a hydroxyethyl group (—CH ₂ CH ₂ OH). Substitution yields intermediate 3ie. This reaction can be performed, for example, in dehydrated acetonitrile (dry-CH ₃ CN) in the presence of potassium carbonate.

  Next, as shown in the following reaction formula 4ie, the intermediate 3ie and sulfuric acid are reacted to convert imide potassium to imidic acid, and then reacted with lithium hydroxide to obtain the intermediate 4ie. This reaction can be performed, for example, by washing an ethyl acetate solution of intermediate 3ie with an aqueous sulfuric acid solution and then adding lithium hydroxide.

Finally, as shown in the following reaction formula 1e, the hydroxy group of the intermediate 4ie is reacted with the isocyanate group of 3- (trialkoxysilyl) propyl isocyanate to form a urethane bond. Let Thereby, the reactive fluorine-containing sulfonylimide 1e is produced. This reaction can be performed, for example, in a mixed solvent containing dehydrated acetonitrile (dry-CH ₃ CN) in the presence of dibutyltin dilaurate (DBTL).

The reactive fluorine-containing sulfonylimide in which A ⁺ is an onium cation is obtained by, for example, mixing the intermediate 3ie and the onium cation solution to replace the potassium ion and the onium cation of the intermediate 3ie to form an onium salt. obtain. Subsequently, it can synthesize | combine by making the hydroxyl group of onium salt and the isocyanate group of 3- (trialkoxysilyl) propyl isocyanate react, and forming a urethane bond.

  Further, X is a reactive fluorine-containing sulfonylimide containing an iminoalkylene group, for example, by reacting intermediate 1ie with alkylenediamine to form an intermediate having an amino group at the terminal, and then the intermediate and chloride. Lithium is reacted to obtain a lithium salt. Thereafter, it can be synthesized by reacting an amino group with 3-glycidoxypropyltrimethoxysilane or the like. Examples of the alkylene diamine include ethylene diamine, 1,4-diaminobutane, 1,6-diaminohexane, and 1,7-diaminoheptane.

  The reactive fluorine-containing sulfonylimide of the present embodiment has a trialkoxysilyl group that is a reactive functional group, and the fluorine-containing sulfonylimide salt that is an anion component is fixed to the resin or mixed with the resin as a polymer. Therefore, bleed out can be prevented. Moreover, since the fluorine-containing sulfonylimide salt has a fluoroalkyl group, when a reactive fluorine-containing sulfonylimide salt is added to the resin, the fluorine-containing sulfonylimide salt easily moves to the surface of the resin composition. Furthermore, since the cation component (alkali metal ion, onium cation) of the fluorine-containing sulfonylimide added to the resin leaves the anion component and moves within the resin, the resin to which the fluorine-containing sulfonylimide salt is added is conductive. Improves and becomes difficult to be charged. Due to these effects, the reactive fluorine-containing sulfonylimide of the present embodiment can be advantageously used as an antistatic agent.

<Reactive fluorine-containing sulfonylimide polymer>
The reactive fluorine-containing sulfonylimide polymer of this embodiment has a repeating unit based on the above-mentioned reactive fluorine-containing sulfonylimide. The reactive fluorine-containing sulfonylimide polymer may be a homopolymer of a reactive fluorine-containing sulfonylimide, or a reactive fluorine-containing sulfonylimide polymer and a monomer other than the reactive fluorine-containing sulfonylimide. A copolymer may also be used.

  The other monomer preferably has a reactive functional group capable of reacting with the reactive functional group (alkoxysilyl group) of the reactive fluorine-containing sulfonylimide. Examples of the reactive functional group capable of reacting with the alkoxysilyl group include an alkoxysilyl group, a silanol group, and a chlorosilyl group.

  The method for synthesizing the reactive fluorine-containing sulfonylimide polymer is not particularly limited, and for example, a known polymerization method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, or a solution polymerization method can be used.

  When the reactive fluorine-containing sulfonylimide polymer of the present embodiment is added to the resin in the same manner as the above-mentioned reactive fluorine-containing sulfonylimide, the cation component (alkali metal ion, onium cation) desorbed from the repeating unit based on the fluorine-containing sulfonylimide. ) Moves through the resin. For this reason, the resin to which the reactive fluorine-containing sulfonylimide polymer of the present embodiment is added has improved conductivity and is difficult to be charged. Moreover, since the reactive fluorine-containing sulfonylimide polymer of this embodiment has a large molecular weight compared with the above-mentioned reactive fluorine-containing sulfonylimide, when it adds to resin, it can prevent a bleed out more. For this reason, by adding a reactive fluorine-containing sulfonylimide copolymer to the resin as an antistatic agent, an excellent antistatic effect can be exhibited stably over a long period of time.

[Antistatic agent]
The antistatic agent of this embodiment contains the polymer which has a repeating unit based on the above-mentioned reactive fluorine-containing sulfonylimide or reactive fluorine-containing sulfonylimide. The antistatic agent of this embodiment can be advantageously used as an antistatic agent for resin molded products such as cases of electronic devices and protective films. The antistatic agent may be contained in the resin molded product, or may be applied to the surface of the resin molded product.

  A resin molded product containing an antistatic agent can be produced by a method in which a matrix resin serving as a base material of a resin molded product is mixed with an antistatic agent, and the resulting mixture is molded. As the matrix resin, for example, silicone resin, acrylic resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, fluorine resin, and polyolefin resin can be used. The amount of the repeating unit based on the reactive fluorine-containing sulfonylimide or the reactive fluorine-containing sulfonylimide contained in the resin molded article is preferably in the range of 0.01% by mass to 30% by mass, particularly preferably 0.1% by mass. % Or more and 10% by mass or less.

  In addition, when reactive fluorine-containing sulfonylimide is used as an antistatic agent, the reactive fluorine-containing sulfonylimide and the raw material monomer of the matrix resin are mixed, and the raw material monomer in the obtained mixture is polymerized to form a matrix resin. Then, a resin molded product may be produced using a method of molding the mixture. The raw material monomer may have a reactive functional group capable of reacting with the reactive functional group (alkoxysilyl group) of the reactive fluorine-containing sulfonylimide. When the raw material monomer has a reactive functional group capable of reacting with an alkoxysilyl group, a resin molded product in which a reactive fluorine-containing sulfonylimide and a matrix resin are bonded can be obtained. On the other hand, when the raw material monomer does not have a reactive functional group capable of reacting with an alkoxysilyl group, a resin molded product in which a reactive fluorine-containing sulfonylimide is dispersed in a matrix resin can be obtained.

  When applying the antistatic agent to the surface of the resin molded product, an antistatic agent solution in which the antistatic agent is dissolved in a solvent is applied to the surface of the resin molded product. The solvent of the antistatic agent solution can be used without particular limitation as long as it dissolves a polymer having a repeating unit based on reactive fluorine-containing sulfonylimide or reactive fluorine-containing sulfonylimide. As the solvent for the reactive fluorine-containing sulfonylimide, for example, an ester solvent, an ether solvent, a nitrile solvent, or a ketone solvent can be used. Examples of ester solvents include ethyl acetate, isopropyl acetate, butyl acetate and the like. The ether solvent may be chain-like or cyclic. Examples of chain ether solvents include diethyl ether, diisopropyl ether, t-butyl methyl ether, cyclopentyl methyl ether, dimethoxymethane, and 1,2-dimethoxyethane. Examples of the cyclic ether solvent include tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 4-methyl-1,3-dioxolane. Examples of nitrile solvents include acetonitrile, isobutyronitrile, valeronitrile, and benzonitrile. Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diisobutyl ketone. Examples of the solvent for the polymer having a repeating unit based on reactive fluorine-containing sulfonylimide or reactive fluorine-containing sulfonylimide include, for example, hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, ether solvents, nitrile solvents A solvent and a ketone solvent can be used. Examples of the hydrocarbon solvent include normal hexane, cyclohexane, toluene, xylene and the like. Examples of the halogenated hydrocarbon solvent include dichloromethane, chloroform, dichloropentafluoropropane, and the like. Examples of the ester solvent, the ether solvent, the nitrile solvent, and the ketone solvent are the same as in the case of the reactive fluorine-containing sulfonylimide described above.

  The antistatic agent solution may further contain other additives as required. Examples of other additives include crosslinking agents, viscosity modifiers, antifoaming agents, antioxidants, plasticizers, flame retardants, infrared absorbers, ultraviolet absorbers, pH adjusters, chelating agents, and colorants. be able to. In addition, when a reactive fluorine-containing sulfonylimide solution is used as an antistatic agent, it contains a monomer having a reactive functional group capable of reacting with the reactive functional group (alkoxysilyl group) of the reactive fluorine-containing sulfonylimide. Further, a polymerization catalyst may be included.

  Since the antistatic agent of the present embodiment includes a polymer having a repeating unit based on the above-mentioned reactive fluorine-containing sulfonylimide or reactive fluorine-containing sulfonylimide, the resin composition contains the polymer or a resin molded product. By applying to the surface, the surface resistivity of the resin composition can be reduced, and static electricity can be hardly charged. Moreover, since the antistatic agent of this embodiment is hard to bleed out, it can exhibit the excellent antistatic effect stably over a long period of time.

  While the embodiments of the present invention have been described above, the technical scope of the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention.

Next, the function and effect of the present invention will be described with reference to examples. The structure of the compound obtained in this example was confirmed by proton nuclear magnetic resonance spectrum ( ¹ H-NMR) and fluorine nuclear magnetic resonance spectrum ( ¹⁹ F-NMR).

[Synthesis Example 1] Synthesis of reactive fluorine-containing sulfonylimide 1 (synthesis of intermediate 1i)
In a flask equipped with a thermometer and a reflux tube, 152 g (0.48 mol) of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride and 36 g of potassium fluoride ( 0.63 mol), dehydrated acetonitrile was charged at a rate of 480 g, and heated to 60 ° C. in a nitrogen atmosphere. Subsequently, 84 g of potassium trifluoromethanesulfonamide was added in several portions, and further heated at 60 ° C. for 2 hours to generate an intermediate 1i by the reaction of the following reaction scheme 1i. After completion of the reaction, insoluble matters were filtered off by suction filtration, and the filtrate was concentrated to dryness to obtain 213 g of a crude product. After adding 109 g of ethanol to the obtained crude product and heating and dissolving at 60 ° C., the insoluble material was filtered off with a 3 μm membrane filter, and the filtrate was added to 2004 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to obtain a white solid intermediate 1i. The amount of intermediate 1i obtained was 192 g (yield: 89%).

( ¹⁹ F-NMR measurement result of intermediate 1i)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ 45.0 (m, 1F), −80.2 (s, 3F), −107.4 (m, 2F), −113.6 (t, 2F) , -119.0 (t, 2F)

(Synthesis of Intermediate 2i)
A flask equipped with a thermometer and a reflux tube was charged with 180 g (0.37 mol) of intermediate 1i, 69 g (3.2 mol) of potassium fluoride and 360 g of dehydrated tetrahydrofuran, and heated to 60 ° C. in a nitrogen atmosphere. did. Then, 201 g (CH ₃ NH ₂ 14 g, 0.45 mol) having a concentration of 2 mol / L of methylamine / tetrahydrofuran solution was dropped, and then heated at 60 ° C. for 2.5 hours. Body 2i was generated. After completion of the reaction, the mixture was concentrated to dryness, and 1498 g of ethyl acetate and 220 g of ion exchange water were added to the residue and mixed, followed by liquid separation to recover the ethyl acetate phase. The recovered ethyl acetate phase was further washed three times with 100 g of a 20% strength by weight aqueous potassium hydroxide solution and three times with 100 g of a 20% strength by weight aqueous potassium chloride solution, and then concentrated to dryness again. The resulting residue was dissolved by adding the same mass of acetonitrile to obtain 199 g of an intermediate 2i acetonitrile solution (solid content 99 g, yield: 100%) that was light yellow and transparent.

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 2i)
¹ H-NMR (400 MHz, D ₂ O): δ2.8 (s, 3H)
¹⁹ F-NMR (376 MHz, D ₂ O): δ-79.1 (s, 3F), -112.1 (t, 2F), -112.4 (t, 2F), -119.1 (t, 2F)

(Synthesis of Intermediate 3i)
In a flask equipped with a thermometer and a reflux tube, 180 g (solid content 90 g, 0.17 mol) of an intermediate 2i acetonitrile solution having a concentration of 50% by mass, 34 g (0.42 mol) of 2-chloroethanol, and 21 g of potassium carbonate (0.15 mol) and dehydrated acetonitrile were charged at a rate of 180 g, and heated at 80 ° C. for 43 hours in a nitrogen atmosphere to generate an intermediate 3i by the reaction of the following reaction formula 3i. After completion of the reaction, insoluble matter was filtered off by suction filtration, the filtrate was concentrated to dryness, 705 g of ethyl acetate and 125 g of 10% strength by weight potassium chloride aqueous solution were added to and mixed with the residue, and the mixture was separated to give acetic acid. The ethyl phase was recovered. The recovered ethyl acetate phase was further washed twice with 100 g of ion-exchanged water and then concentrated to dryness to obtain a crude product. The obtained crude product was dissolved by adding 97 g of ethanol, and the resulting solution was added to 1013 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to obtain a white solid intermediate 3i. The amount of intermediate 3i obtained was 75 g (yield: 79%).

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 3i)
¹ H-NMR (400 MHz, D ₂ O): δ 3.8-3.3 (m, 4H), 3.1 (s, 3H)
¹⁹ F-NMR (376 MHz, D ₂ O): δ-79.2 (s, 3F), -111.3 (m, 2F), -112.5 (t, 2F), -119.1 (t, 2F)

(Synthesis of Intermediate 4i)
In a separatory funnel, 20 g (38 mmol) of Intermediate 3i was weighed, and 60 g of sulfuric acid aqueous solution having a concentration of 40% by mass and 206 g of ethyl acetate were added and mixed, and then separated to recover the upper phase. The recovered upper phase was washed twice with 60 g of a 40% by mass sulfuric acid aqueous solution. After washing, 30 g of a lithium hydroxide aqueous solution having a concentration of 10% by mass was added and mixed to form an intermediate 4i by the reaction of the following reaction formula 4i, followed by liquid separation to recover the upper phase. The recovered upper phase was washed twice with 20 g of ion-exchanged water, concentrated, and acetonitrile was added to obtain 36 g (yield: 96%) of an acetonitrile solution of intermediate 4i having a concentration of 50% by mass.

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 4i)
¹ H-NMR (400 MHz, D ₂ O): δ 4.0-3.3 (m, 4H), 3.2 (s, 3H)
¹⁹ F-NMR (376 MHz, D ₂ O): δ-79.3 (s, 3F), -111.4 (m, 2F), -112.6 (t, 2F), -119.1 (t, 2F)

(Synthesis of reactive fluorine-containing sulfonylimide 1)
In a flask equipped with a thermometer and a reflux tube, 10.0 g (50 g, 9.9 mmol) of an acetonitrile solution of 50 mass% intermediate 4i, 0.09 g of dibutyltin dilaurate, and dehydrated acetonitrile were added. The mixture was charged at a rate of 15 g and heated to 50 ° C. in a nitrogen atmosphere. 4 g (0.017 mol) of 3- (triethoxysilyl) propyl isocyanate was added dropwise thereto, and then heated at 60 ° C. for 1 hour to produce a reactive fluorine-containing sulfonylimide 1 by the reaction of the following reaction formula 1. I let you. After completion of the reaction, acetonitrile was distilled off, and 3 g of dehydrated ethanol and 42 g of toluene were added to the residue and mixed, followed by liquid separation to recover the lower phase. The recovered lower phase is further washed with 32 g of toluene, and then concentrated. Then, dehydrated ethyl acetate is added, and a reactive fluorine-containing sulfonylimide having a triethoxysilyl group as a reactive functional group and lithium as a cation component 9.4 g (yield: 68%) of an ethyl acetate solution in which 1 was dissolved at a concentration of 50% by mass was obtained.

( ¹ H-NMR measurement result and ¹⁹ F-NMR measurement result of reactive fluorine-containing sulfonylimide 1)
¹ H-NMR (400 MHz, CD ₃ CN): δ 4.4-3.2 (m, 4H), 3.8 (q, 6H), 3.1 (s, 3H), 3.1 (q, 2H) ), 1.6 (m, 2H), 1.2 (t, 9H), 0.6 (m, 2H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-80.2 (s, 3F), -111.8 (m, 2F), -113.4 (t, 2F), -119.5 (q, 2F)

[Synthesis Example 2] Synthesis of reactive fluorine-containing sulfonylimide 2 (synthesis of intermediate 5i)
In a flask equipped with a thermometer and a reflux tube, 343 g (1.59 mol) of 1,1-difluoromethane-1,1-disulfonyldifluoride, 115 g (1.97 mol) of potassium fluoride, and 1627 g of dehydrated acetonitrile And heated to 60 ° C. in a nitrogen atmosphere. Next, after adding 509 g (1.51 mol) of nonafluorobutanesulfonamide potassium in several portions, the mixture was further heated at 60 ° C. for 2 hours to generate an intermediate 5i by the reaction of the following reaction formula 5i. After completion of the reaction, insoluble matters were filtered off by suction filtration, and the filtrate was concentrated to dryness to obtain 789 g of a crude product. After adding 397 g of ethanol to the obtained crude product and heating and dissolving at 60 ° C., the insoluble matter was filtered off with a 3 μm membrane filter, and the filtrate was added to 4032 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to obtain a white solid intermediate 5i. The amount of the obtained intermediate 5i was 700 g (yield: 87%).

( ¹⁹ F-NMR measurement result of intermediate 5i)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ 45.0 (m. 1F), −80.9 (t, 3F), −101.8 (s, 2F), −112.6 (t, 2F) , -120.5 (m, 2F), -125.4 (m, 2F)

(Synthesis of Intermediate 6i)
A flask equipped with a thermometer and a reflux tube was charged with 443 g (0.83 mol) of intermediate 5i, 147 g (2.53 mol) of potassium fluoride, and 802 g of dehydrated tetrahydrofuran, and heated to 60 ° C. in a nitrogen atmosphere. did. Thereto, 59.1 g (1.00 mol) of propylamine was dropped, and the mixture was heated at 60 ° C. for 2.5 hours to generate an intermediate 6i by the reaction of the following reaction formula 6i. After completion of the reaction, the mixture was concentrated to dryness, 2417 g of ethyl acetate and 360 g of ion-exchanged water were added to and mixed with the residue, and the phases were separated to recover the ethyl acetate phase. The recovered ethyl acetate phase was further washed twice with 200 g of a 20% strength by weight aqueous potassium hydroxide solution and twice with 220 g of a 20% strength by weight aqueous potassium chloride solution, and then concentrated and dried again. The same amount of acetonitrile was added to the resulting residue to dissolve, and 982 g (solid content 491 g, yield: 97%) of an acetonitrile solution of intermediate 6i having a light yellow and transparent concentration of 50% by mass was obtained.

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 6i)
¹ H-NMR (400 MHz, D ₂ O): δ 3.3 (t, 2H), 1.5 (m, 2H), 0.9 (t, 3H)
¹⁹ F-NMR (376 MHz, D ₂ O): δ-80.7 (t, 3F), -106.5 (s, 2F), -111.4 (t, 2F), -120.3 (m, 2F), -125.0 (m, 2F)

(Synthesis of Intermediate 7i)
In a flask equipped with a thermometer and a reflux tube, 684 g (solid content 342 g, 0.56 mol) of acetonitrile solution of intermediate 6i having a concentration of 50 mass%, 6-chloro-1-hexanol 212 g (1.55 mol), carbonic acid 80 g (0.58 mol) of potassium and 433 g of dehydrated acetonitrile were charged and heated in a nitrogen atmosphere at 80 ° C. for 48 hours to produce intermediate 7i by the reaction of the following reaction formula 7i. After completion of the reaction, insoluble matter was filtered off by suction filtration, and the filtrate was concentrated to dryness. 1840 g of ethyl acetate was added to the resulting residue to dissolve it, and the resulting solution was washed twice with 300 g of a 10% strength by weight aqueous potassium chloride solution and then separated to recover the ethyl acetate phase. The recovered ethyl acetate phase was further washed twice with 300 g of ion-exchanged water and then concentrated to dryness to obtain a crude product. The obtained crude product was dissolved by adding 203 g of ethanol, and the obtained solution was added to 2032 g of chloroform to crystallize the product. The crystallized product was collected by suction filtration and dried to obtain a white solid intermediate 7i. The amount of intermediate 7i obtained was 327 g (yield: 87%).

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 7i)
¹ H-NMR (400 MHz, CD ₃ CN): δ 3.8-3.3 (m, 6H), 1.8-1.3 (m, 10H), 1.0 (t, 3H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-80.7 (t, 3F), -107.3 (s, 2F), -111.5 (t, 2F), -120.4 (m, 2F), -125.0 (m, 2F)

(Synthesis of Intermediate 8i)
In a separatory funnel, 250 g (371 mmol) of the intermediate 7i was weighed, and 504 g of sulfuric acid aqueous solution having a concentration of 40% by mass and 2513 g of ethyl acetate were added and mixed, and then separated to recover the upper phase. The recovered upper phase was washed twice with 60 g of a 40% by mass sulfuric acid aqueous solution. After washing, 30 g of a lithium hydroxide aqueous solution having a concentration of 10% by mass was added and mixed to form an intermediate 8i by the reaction of the following reaction formula 8i, followed by liquid separation to recover the upper phase. The recovered upper phase was washed twice with 750 g of ion-exchanged water, concentrated, and acetonitrile was added to obtain 36 g (yield: 96%) of an acetonitrile solution of intermediate 8i having a concentration of 50% by mass.

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 8i)
¹ H-NMR (400 MHz, CD ₃ CN): δ 4.0-3.3 (m, 6H), 1.8-1.3 (m, 10H), 1.0 (t, 3H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-80.5 (t, 3F), −107.7 (s, 2F), −111.9 (t, 2F), −120.7 (m, 2F), -125.2 (m, 2F)

(Synthesis of reactive fluorine-containing sulfonylimide 2)
In a flask equipped with a thermometer and a reflux tube, an acetonitrile solution of intermediate 8i having a concentration of 50% by mass (solid content 200 g, 0.31 mol), dibutyltin dilaurate 0.1 g, dehydrated acetonitrile 398 g Charged and heated to 50 ° C. under nitrogen atmosphere. Thereto, 100 g (0.41 mol) of 3- (triethoxysilyl) propyl isocyanate was added dropwise and heated at 60 ° C. for 1 hour to produce a reactive fluorine-containing sulfonylimide 2 by the reaction of the following reaction formula 2. I let you. After completion of the reaction, acetonitrile was distilled off, 143 g of dehydrated ethanol and 1834 g of toluene were added to the residue, and the mixture was separated to recover the lower phase. The recovered lower phase was further washed with 1368 g of toluene and then concentrated, and then dehydrated ethyl acetate was added, and a reactive fluorine-containing sulfonylimide having a triethoxysilyl group as a reactive functional group and lithium as a cation component 432 g (yield: 78%) of an ethyl acetate solution in which 2 was dissolved at a concentration of 50% by mass was obtained.

( ¹ H-NMR measurement result and ¹⁹ F-NMR measurement result of reactive fluorine-containing sulfonylimide 2)
¹ H-NMR (400 MHz, CD ₃ CN): δ 4.3-3.3 (m, 12H), 3.1 (q, 2H), 1.8-1.3 (m, 12H), 1.2 (T, 9H), 1.0 (t, 3H), 0.6 (m, 2H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-79.8 (t, 3F), -106.9 (s, 2F), -111.0 (t, 2F), -119.8 (m, 2F), -124.4 (m, 2F)

[Synthesis Example 3] Synthesis of reactive fluorine-containing sulfonylimide 3 (synthesis of intermediate 9i)
A flask equipped with a thermometer and a reflux tube was charged with 37 g (0.62 mol) of ethylenediamine and 203 g of dehydrated acetonitrile and heated to 60 ° C. in a nitrogen atmosphere. Thereto was added dropwise 200 g of a solution prepared by dissolving the intermediate 1i synthesized in Synthesis Example 1 in the same amount of dehydrated acetonitrile (amount of intermediate 1i: 100 g, 0.21 mol), and then 2.5 ° C. at 60 ° C. Sulfonamide was produced by heating for a period of time. After completion of the heating, the mixture was concentrated to dryness, 854 g of ethyl acetate and 87 g of ion-exchanged water were added to and mixed with the residue, and the phases were separated to recover the ethyl acetate phase. The recovered ethyl acetate phase was washed three times with 100 g of a 20% strength by weight aqueous potassium hydroxide solution, so that the sulfonamide was potassium chlorided to produce an intermediate 9i as shown in the following reaction formula 9i. Next, the ethyl acetate phase produced by the intermediate 9i was washed twice with 100 g of a 20% strength by weight aqueous potassium chloride solution and once with 30 g of a 40% strength by weight sulfuric acid aqueous solution, and then concentrated to dryness. To the obtained residue, 300 g of tetrahydrofuran and 88 g of potassium carbonate were added and stirred at 60 ° C. for 2 hours, and then insoluble matter was filtered off by suction filtration. The filtrate was concentrated to a tetrahydrofuran solution of intermediate 9i having a concentration of 50% by mass to obtain 224 g of a pale yellow transparent solution (solid content: 112 g, yield: 96%).

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 9i)
¹ H-NMR (400 MHz, CD ₃ CN): δ 3.0 (m, 2H), 2.6 (t, 2H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-80.2 (s, 3F), -111.3 (t, 2F), -113.4 (t, 2F), -119.1 (t, 2F)

(Synthesis of Intermediate 10i)
In a flask equipped with a thermometer and a reflux tube, 200 g (solid content 100 g, 0.35 mol) of a 50 mass% intermediate 9i tetrahydrofuran solution, lithium chloride 45 g (1.07 mol), and dehydrated tetrahydrofuran at a ratio of 203 g. The mixture was heated at 60 ° C. for 15 hours under a nitrogen atmosphere to generate intermediate 10i by the reaction of the following reaction formula 10i. After completion of the reaction, insoluble matters were filtered off by suction filtration, and the filtrate was concentrated to obtain 377 g of tetrahydrofuran solution (solid content: 189 g, yield: 100%) having a concentration of intermediate 10i of 50% by mass.

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 10i)
¹ H-NMR (400 MHz, CD ₃ CN): δ 3.0 (m, 2H), 2.6 (t, 2H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-80.3 (s, 3F), -111.4 (t, 2F), -113.6 (t, 2F), -119.3 (t, 2F)

(Synthesis of reactive fluorine-containing sulfonylimide 3)
A flask equipped with a thermometer and a reflux tube was charged with 122 g (solid content 61 g, 0.119 mmol) of a 50 mass% intermediate 10i tetrahydrofuran solution and 120 g of dehydrated tetrahydrofuran at 60 ° C. under a nitrogen atmosphere. Heated. Thereto, 29 g (0.12 mol) of 3-glycidoxypropyltrimethoxysilane was added dropwise, and then heated at 60 ° C. for 2 hours to produce reactive fluorine-containing sulfonylimide 3 by the reaction of the following reaction formula 3. It was. After completion of the reaction, the mixture was concentrated to dryness, and 78 g of dehydrated ethanol and 1230 g of toluene were added to and mixed with the residue, followed by liquid separation to recover the lower phase. The recovered lower phase was further washed with 935 g of toluene and then concentrated, and then dehydrated ethyl acetate was added, and a reactive fluorine-containing sulfonylimide having a trimethoxysilyl group as a reactive functional group and lithium as a cation component 144 g (yield: 81%) of an ethyl acetate solution in which 3 was dissolved at a concentration of 50% by mass was obtained.

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of the reactive fluorinated sulfonylimide 3)
¹ H-NMR (400 MHz, CD ₃ CN): δ 4.4-3.2 (m, 4H), 3.9 (m, 1H), 3.6 (s, 9H), 3.6 (m, 2H) ), 3.6 (t, 2H), 2.7 (m, 2H), 1.7 (m, 2H), 0.6 (m, 2H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-80.3 (s, 3F), -111.9 (t, 2F), -113.6 (t, 2F), -119.6 (q, 2F)

[Synthesis Example 4] Synthesis of reactive fluorine-containing sulfonylimide 4 (synthesis of intermediate 11i)
10.1 g (0.0188 mol) of intermediate 3i synthesized in Synthesis Example 1 was added to 10.5 g of ion-exchanged water, and intermediate 3i was dissolved to prepare an intermediate 3i aqueous solution. The prepared intermediate 3 aqueous solution was put into a separating funnel, and 8.7 g (solid content 4.4 g, 0.0244 mol) of N-ethyl-N-methylpyrrolidinium bromide aqueous solution having a concentration of 50% by mass and chloroform were added thereto. 17.8 g was added and mixed to produce intermediate 10i by the reaction of the following reaction formula 11i, followed by liquid separation to recover the lower phase. The recovered lower phase was washed 4 times with 10 g of ion-exchanged water, and then insoluble matter was filtered off by suction filtration. The filtrate was concentrated to give intermediate 11i. The amount of intermediate 11i obtained was 6.7 g (yield: 58%).

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of Intermediate 11i)
¹ H-NMR (400 MHz, CD ₃ CN): δ 3.8-3.2 (m, 4H), 3.4 (m, 4H), 3.3 (q, 2H), 3.1 (s, 3H) ), 2.9 (s, 3H), 2.1 (m, 4H), 1.3 (t-t, 3H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-80.2 (s, 3F), -111.8 (m, 2F), -113.4 (t, 2F), -119.5 (t, 2F)

(Synthesis of reactive fluorine-containing sulfonylimide 4)
A flask equipped with a thermometer and a reflux tube was charged with 5.1 g (9.1 mmol) of intermediate 11i, 0.08 g of dibutyltin dilaurate, and 15.1 g of dehydrated acetonitrile at 50 ° C. in a nitrogen atmosphere. Heated. Thereto, 3.9 g (15.8 mmol) of 3- (triethoxysilyl) propyl isocyanate was added dropwise, and then heated at 60 ° C. for 1 hour. Was generated. After completion of the reaction, acetonitrile was distilled off, and 3 g of dehydrated ethanol and 54 g of toluene were added to the residue and mixed, followed by liquid separation to recover the lower phase. The recovered lower phase is further washed with 38 g of toluene, and then concentrated to have reactive fluorine-containing reactive fluorine containing triethoxysilyl group as a reactive functional group and N-ethyl-N-methylpyrrolidinium as a cation component. The sulfonylimide 4 was obtained. The amount of the obtained reactive fluorine-containing sulfonylimide 4 was 6.2 g (yield: 84%).

⁽¹ H-NMR measurement results and the ¹⁹ F-NMR measurement results of the reactive fluorinated sulfonylimide 4)
¹ H-NMR (400 MHz, CD ₃ CN): δ 4.4-3.3 (m, 16H), 3.1 (s, 3H), 3.1 (q, 2H), 2.9 (s, 3H) ), 2.1 (m, 4H), 1.6 (m, 2H), 1.3 (t-t, 3H), 1.2 (t, 9H) 0.6 (m, 2H)
¹⁹ F-NMR (376 MHz, CD ₃ CN): δ-80.2 (s, 3F), -111.9 (t, 2F), -113.5 (t, 2F), -119.5 (q, 2F)

[Synthesis Example 5] Synthesis of Copolymer 1 In a flask equipped with a thermometer and a reflux tube, 40 g of an ethyl acetate solution of the reactive fluorine-containing sulfonylimide 1 having a concentration of 50% by mass obtained in Synthesis Example 1 (solid content 20 g, 27 mmol) and concentrated under a nitrogen atmosphere. The residue was dissolved in 27 g of 1-propanol, and 29 g (195 mmol) of diethoxydimethylsilane and 10 g (55 mmol) of triethoxymethylsilane were added to the obtained solution and mixed. After heating up the obtained liquid mixture to 60 degreeC, 6 g of hydrochloric acid with a density | concentration of 0.1 mol / L was dripped at the liquid mixture. Thereafter, the mixture was further heated at 60 ° C. for 18 hours to react the mixed solution. The obtained reaction mixture was concentrated, and the residue was washed twice with 60 g of n-hexane and then concentrated to obtain 21 g of copolymer 1 having a reactive fluorine-containing sulfonylimide 1 content of 34% by mass. .

[Synthesis Example 6] Synthesis of Copolymer 2 In a flask equipped with a thermometer and a reflux tube, 200 g of an ethyl acetate solution of reactive fluorine-containing sulfonylimide 2 having a concentration of 50% by mass obtained in Synthesis Example 2 (solid content: 100 g, 113 mmol) and concentrated under a nitrogen atmosphere. The residue was dissolved in 136 g of 1-propanol, and 122 g (826 mmol) of diethoxydimethylsilane and 42 g (233 mmol) of triethoxymethylsilane were added to the resulting solution and mixed. After heating up the obtained liquid mixture at 60 degreeC, 30 g of hydrochloric acid with a density | concentration of 0.1 mol / L was dripped at the liquid mixture. Thereafter, the mixture was further heated at 60 ° C. for 15 hours to react the mixed solution. The obtained reaction mixture was concentrated, and the residue was washed twice with 273 g of n-hexane and then concentrated to obtain 95 g of copolymer 2 having a reactive fluorine-containing sulfonylimide 2 content of 38% by mass. .

[Synthesis Example 7] Synthesis of Copolymer 3 In a flask equipped with a thermometer and a reflux tube, 100 g of an ethyl acetate solution of the reactive fluorine-containing sulfonylimide 3 having a concentration of 50% by mass obtained in Synthesis Example 3 (solid content 50 g, 65 mmol), and concentrated under a nitrogen atmosphere. The residue was dissolved in 68 g of 1-propanol, and 58 g (479 mmol) of dimethyldimethoxysilane and 18 g (135 mmol) of methyltrimethoxysilane were mixed with the obtained solution. The obtained mixed solution was heated to 40 ° C., and 15 g of hydrochloric acid having a concentration of 0.1 mol / L was added dropwise to the mixed solution. Then, it heated at 40 degreeC for 15 hours, and made the liquid mixture react. The obtained reaction mixture was concentrated, and the residue was washed twice with 136 g of n-hexane and then concentrated to obtain 57 g of copolymer 3 having a reactive fluorine-containing sulfonylimide 3 content of 40% by mass.

[Synthesis Example 8] Synthesis of Copolymer 4 5 g (6 mmol) of the reactive fluorine-containing sulfonylimide 4 obtained in Synthesis Example 4 was charged into a flask equipped with a thermometer and a reflux tube, and 1-propanol was added in a nitrogen atmosphere. 7 g was added to dissolve the reactive fluorine-containing sulfonylimide 4. Next, 7 g (45 mmol) of diethoxydimethylsilane and 2 g (13 mmol) of triethoxymethylsilane were added to the obtained solution and mixed. After the temperature of the obtained mixed liquid was raised to 60 ° C., 2 g of hydrochloric acid having a concentration of 0.1 moml / L was added dropwise to the mixed liquid, and then the mixture was further reacted by heating at 60 ° C. for 18 hours. The obtained reaction mixture was concentrated, and the residue was washed twice with 15 g of n-hexane and then concentrated to obtain 5 g of copolymer 4 having a reactive fluorine-containing sulfonylimide 4 content of 36% by mass.

[Invention Example 1]
The copolymer 1 synthesized in Synthesis Example 5 was dissolved in 0.003 g of a silicone resin (KE-4897-T, manufactured by Shin-Etsu Chemical Co., Ltd.) in an amount of 1 g in 99 g of ethyl acetate. The obtained solution was applied to the surface of a PET film (Lumirror 100T60, manufactured by Panac Co., Ltd.) using a bar coater (No. 16). The obtained PET film with a coating film was allowed to stand overnight in an environment of 60 ° C. to cure the coating film, so that the content of copolymer 1 was 0.3% by mass (reactive fluorine-containing sulfonylsulfonyl). A silicone resin composition film having an imide 1 content of 0.1% by mass was obtained. The surface resistivity of the obtained silicone resin composition film was measured using Hirestar (manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The results are shown in Table 1.

[Invention Example 2]
The content rate of the copolymer 1 is 3 mass% (the content rate of the reactive fluorine-containing sulfonylimide 1 is 1 mass) in the same manner as in Example 1 except that the addition amount of the copolymer 1 is 0.029 g. %) Silicone resin composition film was prepared, and the surface resistivity of the obtained silicone resin composition film was measured. The results are shown in Table 1.

[Invention Example 3]
The content of the copolymer 1 is 15% by mass (the content of the reactive fluorine-containing sulfonylimide 1 is 5% by mass) in the same manner as in Example 1 except that the addition amount of the copolymer 1 is 0.147 g. %) Silicone resin composition film was prepared, and the surface resistivity of the obtained silicone resin composition film was measured. The results are shown in Table 1.

[Invention Examples 4 to 12]
A silicone resin composition film was prepared and obtained in the same manner as in Example 1 except that copolymers 2 to 4 were added in the amounts shown in Table 1 below instead of copolymer 1. The surface resistivity of the silicone resin composition film was measured. The results are shown in Table 1.

[Comparative Example 1]
A silicone resin film was produced in the same manner as in Example 1 except that the copolymer 1 was not added, and the surface resistivity of the obtained silicone resin film was measured. The results are shown in Table 1.

  From the results in Table 1, Examples 1 to 12 of the present invention containing the reactive fluorine-containing sulfonylimide were compared with the silicone resin film of Comparative Example 1 containing no reactive fluorine-containing sulfonylimide. Was confirmed to be significantly reduced.

Claims (7)

Reactive fluorine-containing sulfonylimide represented by the following general formula (1).

However, in the above general formula (1), R ¹ represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkali metal ion or an onium cation, and R ² represents a methyl group or an ethyl group. Rf ¹ represents a fluorine atom or a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms, and Rf ² represents a linear or branched perfluoroalkylene group having 1 to 4 carbon atoms. X represents a linking group which is a divalent organic group, and A ⁺ represents an alkali metal ion or an onium cation. Wherein Rf ² is reactive fluorinated sulfonylimide according to claim 1, characterized in that a linear perfluoroalkylene group having 3 carbon atoms. The reactive fluorine-containing sulfonylimide according to claim 1 or 2, wherein X is a divalent organic group represented by the following general formula (2).

However, in said general formula (2), * represents a joint with Si. The reactive fluorine-containing sulfonylimide according to any one of claims 1 to 3, wherein the A ⁺ is an alkali metal ion.   The antistatic agent containing the reactive fluorine-containing sulfonylimide of any one of Claims 1-4.   A polymer comprising a repeating unit based on the reactive fluorine-containing sulfonylimide according to any one of claims 1 to 4.   An antistatic agent comprising the polymer according to claim 6.