JP2006307112A - Fluorine-containing polyimide resin, method for producing the same, primer, and resin coating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing polyimide resin having a combination of surface characteristics, mechanical properties, heat resistance and adhesivity, to provide a method for producing the polyimide resin, and to provide a primer and a resin coating method respectively. <P>SOLUTION: The fluorine-containing polyimide resin is represented by the general formula (1) (wherein, R is a perfluoroalkenyl or perfluoroalkyl group; Ar is a bivalent aromatic residue; Ar' is a tetravalent aromatic residue; and n is an integer of 10-200). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a fluorine-containing polyimide resin, a production method thereof, a primer, and a resin coating method, and particularly relates to a fluorine-containing polyimide resin excellent in surface characteristics, mechanical properties, heat resistance, and adhesiveness, a production method thereof, a primer and a resin coating method. It is.

Polyimide resins are known to have high heat resistance and excellent mechanical strength, but there are several points to be improved such as workability. Further, existing fluororesins are excellent in surface properties such as heat resistance and high water repellency, but also have problems in molding processability due to high melting temperature. In order to improve these problems, a series of polymers in which an aromatic diamine and a compound containing a perfluoroalkenyl group or a perfluoroalkyl group are reacted to introduce a fluorine compound into a side chain has been proposed (Patent Document 1). To 3).
JP-A-8-239470 Japanese Patent No. 3538891 Japanese Patent No. 3025952

  However, a fluorine-containing polyimide resin having excellent adhesiveness, mechanical properties, surface properties, and heat resistance, taking advantage of the properties of the polyimide resin and the fluororesin, has not yet been proposed. An object of this invention is to provide the fluorine-containing polyimide resin which has surface characteristics, mechanical characteristics, heat resistance, and adhesiveness, its manufacturing method, a primer, and the resin coating method.

  The fluorine-containing polyimide resin of the present invention has the general formula (1)

(In the formula, R represents a perfluoroalkenyl group or a perfluoroalkyl group, Ar represents a divalent aromatic residue, Ar ′ represents a tetravalent aromatic residue, and n represents an integer of 10 to 200. .) With the above chemical structure, the fluorine-containing polyimide resin of the present invention can have surface characteristics, mechanical characteristics, heat resistance and adhesiveness.

Process for producing a fluorinated polyimide resin according to the present invention, the general formula _{(2), H 2 N-} Ar-NH 2 (2) (Ar is the same. Above) one aromatic diamine represented by or two Silylation of one or more species with one or more silylating agents, and general formula (3)

(Wherein X represents a halogen atom and R is the same as above), one or more triazine dihalides represented by the general formula (4)

(Wherein Ar 'is the same as defined above) is reacted with one or more of the aromatic tetracarboxylic dianhydrides represented by the general formula (1)

(Wherein R, Ar, Ar ′, n are the same as above), a fluorine-containing polyimide resin represented by the following formula is obtained.

In addition, the fluorine-containing polyimide resin of the present invention is one or two or more kinds of silyl of the aromatic diamine represented by the general formula (2) represented by H ₂ N—Ar—NH ₂ (2). Silylated with an agent, and general formula (3)

(Wherein X and R are the same as defined above) and one or more triazine dihalides represented by the general formula (4)

(Wherein Ar 'is the same as above), and is a fluorine-containing polyimide resin obtained by reacting with one or more of aromatic tetracarboxylic dianhydrides.

  The primer of the present invention is one or more of the above-mentioned fluorine-containing polyimide resins or fluorine-containing polyimide resins produced by the above production method (if the above-mentioned fluorine-containing polyimide resin of the present invention is used, the production method of the present invention). It may be a mixture of one type of fluorine-containing polyimide resin produced in the above and another type of fluorine-containing polyimide resin of the present invention, that is, the fluorine-containing polyimide resins according to separate claims of the present invention. And a primer containing a fluororesin. Thereby, a primer having both high chemical resistance and excellent heat resistance can be obtained. As a result, for example, it becomes possible to form a fluororesin coating on the metal surface that can withstand an environment that has not been able to cope with so far.

  In the resin coating method of the present invention, one or two or more of the above-mentioned fluorine-containing polyimide resins or fluorine-containing polyimide resins produced by the above production method (same as above when mixed) are used as a binder. Then, a coated resin is coated on the substrate to be coated. Thus, for example, when a fluorine resin coating (coating resin) is applied to a metal (coating substrate), by using the fluorine-containing polyimide resin as a primer or binder (undercoat layer) of the coating resin, heat resistance, surface characteristics, A fluororesin coat having both mechanical properties and adhesive durability can be formed.

  The fluorine-containing polyimide resin of the present invention can have surface characteristics, mechanical characteristics, heat resistance and adhesion durability, and can be mixed with a fluororesin to obtain a primer excellent in the above-mentioned various characteristics.

  Next, an embodiment of the present invention will be described. The fluorine-containing polyimide resin of the present invention is a resin represented by the above general formula (1). (1) In the formula, R represents a perfluoroalkenyl group or a perfluoroalkyl group, Ar represents a divalent aromatic residue, Ar ′ represents a tetravalent aromatic residue, and n represents an integer of 10 to 200. Indicates. In the above general formula (1), when n is smaller than 10, the properties such as mechanical properties and heat resistance are not sufficient when molded into a film or the like, and when n exceeds 200, solubility in organic solvents and the like are molded. The property becomes insufficient.

The fluorine-containing polyimide resin in the present embodiment is one or two aromatic diamines represented by the general formula (2) represented by H ₂ N—Ar—NH ₂ (2) (Ar is the same as described above). The above is silylated with one or more silylating agents, one or more triazine dihalides represented by the above general formula (3), and the above general formula (4). Obtained by reacting one or more aromatic tetracarboxylic dianhydrides. (3) In the formula, X and R are the same as described above. In the formula (4), Ar ′ is the same as described above.

  In the general formulas (1) and (2), the divalent aromatic residue represented by Ar includes various groups shown in Table 1 below.

  Specific examples of the aromatic diamine represented by the general formula (2) include metaphenylene diamine, paraphenylene diamine, 3,3′-diaminobiphenyl, 4,4′-diaminobiphenyl, and 3,3′-methylene. Dianiline, 4,4′-methylenedianiline, 4,4′-isopropylidenedianiline, 3,3′-oxydianiline, 4,4′-oxydianiline, 3,4′-oxydianiline, 3 , 3′-thiodianiline, 4,4′-thiodianiline, 3,3′-carbonyldianiline, 4,4′-carbonyldianiline, 3,3′-sulfonyldianiline, 4,4′-sulfonyldianiline, 1 , 4-Naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,2-bis (4-aminophenoxyphenyl) propane 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, bis (4-aminophenoxyphenyl) sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 1,3-bis (4-aminophenoxy) ), Benzene, 2,2-bis (4-aminophenyl) hexafluoropropane, and the like. In the embodiment of the present invention, these aromatic diamines are used alone or in combination.

  The above aromatic diamine is dissolved in a solvent and silylated by adding a silylating agent. Examples of the aromatic diamine solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidone, and tetramethylene sulfone, benzene, Aromatic solvents such as anisole, diphenyl ether, nitrobenzene, benzonitrile, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichlorobenzene, tetrahydrofuran (THF), dioxane And ether solvents such as acetone and ketone solvents such as acetone and methyl ethyl ketone.

The reaction between the aromatic diamine dissolved in the solvent and the silylating agent is represented by (reaction formula) H ₂ N—Ar—NH ₂ + 2X—Si (CH ₃ ) ₃ → (CH ₃ ) ₃ SiNH—Ar—NHSi (CH ₃ ) ₃ + 2HX (wherein Ar is the same as above, X represents a halogen atom), or (reaction formula) H ₂ N—Ar—NH ₂ + (CH ₃ ) ₃ Si—Y—Si ( CH ₃ ) ₃ → (CH ₃ ) ₃ SiNH—Ar—NHSi (CH ₃ ) ₃ + YH ₂ (where Ar is the same as above, Y represents NH, CH ₃ CON, CF ₃ CON, etc.). ) Based on. As shown in Table 2, there are various types of silylating agents such as chlorosilane, silylamine, and silylamide, and these can be used.

  The silylamide type is particularly preferable, and for example, N, O-bis (trimethylsilyl) acetamide, N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) or the like can be used. Although acetamide and trifluoroacetamide are by-produced in the system, they are easily removed because they are inactive.

Since the produced silylated aromatic diamine compound represented by the following general formula (5) is excellent in solubility, a wide range of polymerization systems can be selected. In the general formula (5), TMS represents Si (CH ₃ ) ₃ , and Ar is a divalent aromatic residue derived from the aromatic diamine.

  In addition, in the method for producing a fluorine-containing polyimide resin using a silylated aromatic diamine compound, since the elimination component is a neutral and volatile halosilane, no acid acceptor is required and no elimination component remains. The fluorine-containing polyimide resin has high purity and is easy to purify.

  As the silylated aromatic diamine compound, for example, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (HFBAPP) is used as the aromatic diamine, and N, O is used as the silylating agent. When -bis (trimethylsilyl) trifluoroacetamide (BSTFA) is used, N-silylated 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (silylated aromatic diamine compound S1) is obtained. It is done. In addition, for example, when 4,4′-oxydianiline (ODA) is used as the aromatic diamine and N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) is used as the silylating agent, N-silylation 4,4'-oxydianiline (silylated aromatic diamine compound S2) is obtained. Needless to say, the silylated aromatic diamine compound is not limited to the above-mentioned two types, and those represented by the general formula (5) are applicable.

  R in the triazine dihalide represented by the general formula (3) is preferably a perfluoroalkenyl group having 5 to 12 carbon atoms such as a perfluorohexenyl group, a perfluoroheptenyl group, a perfluorooctenyl group, or a perfluorononenyl group. be able to. In addition, a branch having 1 to 18 carbon atoms such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, etc. It may be a perfluoroalkyl group which may have Further, the halogen atom represented by X in the general formula (3) includes fluorine, chlorine, bromine and iodine atoms.

  When the halogen of the triazine dihalide represented by the general formula (3) is chlorine, it may be reacted with perfluoroalkenyloxyaniline (or perfluoroalkyloxyaniline) using cyanuric chloride. In cyanuric chloride, chlorine is bonded to carbons at the 2, 4 and 6 positions, but the elimination of chlorine at each position in the reaction can be controlled because the temperature range is different. What is necessary is just to perform at the reaction temperature of 0-5 degreeC in order to remove | eliminate the chlorine of 4th-position carbon. At this time, cyanuric chloride is dissolved in an organic solvent. Examples of organic solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidone, tetramethylene sulfone, benzene, anisole, Aromatic solvents such as diphenyl ether, nitrobenzene, benzonitrile, halogen solvents such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichlorobenzene, tetrahydrofuran (THF), dioxane, etc. Ether solvents, ketone solvents such as acetone and methyl ethyl ketone can be used.

  In addition, perfluoroalkenyloxyaniline (or perfluoroalkyloxyaniline) added to cyanuric chloride in a state dissolved in the organic solvent is also in a state dissolved in the organic solvent. Examples of the organic solvent for perfluoroalkenyloxyaniline (or perfluoroalkyloxyaniline) include N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidone, and tetramethylene sulfone. Aprotic polar solvents, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, halogens such as chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichlorobenzene Solvents, ether solvents such as tetrahydrofuran (THF) and dioxane, and ketone solvents such as acetone and methyl ethyl ketone can be used.

  In the reaction of the cyanuric chloride and perfluoroalkenyloxyaniline (or perfluoroalkyloxyaniline), the temperature is controlled so as not to greatly exceed the range of 0 to 5 ° C. while adding an aqueous sodium carbonate solution. Thereafter, dehydration is performed using, for example, anhydrous sodium sulfate. In this way 6- (perfluoroalkenyloxyanilino) -1,3,5-triazine-2,4-dichloride (or 6- (perfluoroalkyloxyanilino) -1,3,5-triazine-2, 4-dichloride) can be obtained. In Table 3, 6- (4-perfluorononenyloxyanilino) -1,3,5-triazine-2,4-dichloride is obtained by reacting cyanuric chloride with p-perfluorononenyloxyaniline. The reaction to obtain

  The fluorine-containing triazine dihalide serves as a monomer for the fluorine-containing polyimide resin of the present embodiment. This monomer is added to the silylated aromatic diamine together with the aromatic tetracarboxylic dianhydride described below and incorporated into the polymer in a copolymerization reaction.

  Examples of the aromatic tetracarboxylic dianhydride represented by the general formula (4) include those listed in Table 4.

  Specifically, pyromellitic anhydride (PMDA), biphenyl-3,4,3 ′, 4′-tetracarboxylic dianhydride (BPDA), benzophenone-3,4,3 ′, 4′-tetracarboxylic acid Dianhydride (BTDA), oxydiphthalic dianhydride (ODPA), 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride (6FDA), diphenylsulfone-3,4,3 ′, 1 type, or 2 or more types, such as 4'-tetracarboxylic dianhydride (DSDA), can be used. By adding the aromatic tetracarboxylic dianhydride and the fluorine-containing triazine dihalide (monomer component) to the silylated aromatic diamine compound and subjecting it to copolymerization, the above general formula (1) The fluorine-containing polyimide resin represented by these can be obtained.

  In the above production conditions, the molecular weight of the fluorine-containing polyimide resin represented by the general formula (1) is the aromatic diamine represented by the general formula (2) and the triazine dihalide represented by the general formula (3) ( Monomer component) and aromatic tetracarboxylic dianhydride represented by the general formula (4), the total number of moles of aromatic tetracarboxylic dianhydride and triazine dihalide and aromatic diamine When the number of moles is equal, a high molecular weight polyimide resin is obtained. In addition, the amount of the silylating agent used in this production method is 2 times or more mol with respect to the aromatic diamine in order to form a silylated aromatic diamine compound, but preferably 2 to 4 times mol. Good.

  Although the amount of the solvent is not particularly limited, it is preferable that the obtained polyimide resin has a weight% of 10 wt% to 40 wt%. This is because when the amount of the solvent is small, the polyimide resin is precipitated and a high molecular weight cannot be obtained, and when the amount of the solvent is too large, the high molecular weight cannot be obtained.

  The polymerization temperature ranges from room temperature to 300 ° C, preferably 100 ° C to 180 ° C. The polymerization time is from several minutes to several days, preferably 3 hours to 1 day.

  To a 100 mL three-necked flask equipped with a nitrogen gas inlet tube, a condenser tube, and a Dean-Stark trap, 12.5 mL of distilled and purified N-methyl-2-pyrrolidone (NMP) and 2,2-bis [4- (4-aminophenoxy) ) Phenyl] hexafluoropropane (HFBAPP) 2.592 g (5 mmol) was added and dissolved with stirring. Next, this solution was cooled to 0 ° C., N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) (3.0 mL, 11 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes and further at room temperature for 30 minutes. N-silylated 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (silylated aromatic diamine compound S1) was derived. Thereafter, 0.736 g (2.5 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 6- (4-perfluorononenyloxyanilino) -1,3,5- Add 1.718 g (2.5 mmol) of triazine-2,4-dichloride (monomer component) and stir for 4 hours at room temperature and 24 hours at 160 ° C. in a nitrogen gas stream to react with trimethylsilyl chloride and trimethyl. Silanol was removed from the system together with nitrogen gas.

After the reaction, the yellow and viscous polymerization solution was poured into 400 mL of methanol to precipitate polyimide, and after filtration, dried under reduced pressure at 80 ° C. for 9 hours. The yield was 4.68 g (98% yield). According to the infrared absorption spectrum of polyimide, it is 1781 cm ⁻¹ (imide bond), 1728 cm ⁻¹ (imide bond), 1580 cm ⁻¹ (triazine ring), 1378 cm ⁻¹ (imide bond), 1246 cm ⁻¹ (CF bond). Characteristic absorption was confirmed.

The logarithmic viscosity and molecular weight of this polyimide are shown below.
(1) Logarithmic viscosity: 0.60 dL / g (measured at 30 ° C. in N-methyl-2-pyrrolidone having a concentration of 0.5 g / dL)
(2) Molecular weight [measured by gel permeation chromatography using N-methyl-2-pyrrolidone solution containing lithium bromide (10 mmol / L) in terms of standard polystyrene]
Number average molecular weight (Mn): 77000
Weight average molecular weight (Mw): 162000
Molecular weight distribution (Mw / Mn): 2.10

  This polyimide was dissolved in N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, tetrahydrofuran and 1,4-dioxane at room temperature and dissolved in chloroform by heating.

  This polyimide N-methyl-2-pyrrolidone solution is cast on a glass plate and dried under reduced pressure at 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to produce a yellow transparent polyimide film. did. From the result of the infrared absorption spectrum and elemental analysis of this film, it was confirmed that it was a polyimide film.

The characteristics of this polyimide film are shown below.
(1) Infrared absorption spectrum: 1781 cm ⁻¹ (imide bond), 1728 cm ⁻¹ (imide bond), 1378 cm ⁻¹ (imide bond)
(2) Elemental analysis _{[(C 88 H 45 F 29} N 8 O 9) Calculated as _n]:
Calculated C, 55.36%; H, 2.38%; N, 5.87%
Found C, 55.14%; H, 2.54%; N, 6.04%
(3) Glass transition temperature: 226 ° C. [Differential scanning calorimetry (DSC)]
(4) Thermal expansion coefficient: 67 ppm / ° C. (temperature range of 70 ° C. to 180 ° C.)
(5) Thermal decomposition temperature (thermogravimetric measurement)
5% weight loss temperature: 420 ° C. (in air), 415 ° C. (in nitrogen)
10% weight loss temperature: 440 ° C. (in air), 435 ° C. (in nitrogen)
(6) Tensile test Tensile strength: 72 MPa
Elongation at break: 5%
Tensile modulus: 3.8 MPa
(7) Water contact angle: 103 degrees

  This polyimide film swelled in N-methyl-2pyrrolidone and was insoluble in N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidone, tetrahydrofuran, 1,4-dioxane and chloroform.

  To a 100 mL three-necked flask equipped with a nitrogen gas inlet tube, a condenser tube, and a Dean-Stark trap, 12.5 mL of distilled and purified N-methyl-2-pyrrolidone (NMP) and 2,2-bis [4- (4-aminophenoxy) ) Phenyl] hexafluoropropane (HFBAPP) 2.592 g (5 mmol) was added and dissolved with stirring. Next, this solution was cooled to 0 ° C., N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) (3.0 mL, 11 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes and further at room temperature for 30 minutes. N-silylated 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (silylated aromatic diamine compound S1) was derived. Then, 4.11 ′ (hexafluoroisopropylidene) diphthalic dianhydride (6FDA) 1.111 g (2.5 mmol) and 6- (4-perfluorononenyloxyanilino) -1,3,5-triazine -2,4-dichloride (1.718 g, monomer component) (2.5 mmol) was added, and the mixture was allowed to react by stirring at room temperature for 4 hours and then at 160 ° C. for 24 hours under a nitrogen gas stream. By-produced trimethylsilyl chloride and trimethylsilanol Was removed out of the system together with nitrogen gas.

After the reaction, the yellow and viscous polymerization solution was poured into 400 mL of methanol to precipitate polyimide, and after filtration, dried under reduced pressure at 80 ° C. for 9 hours. The yield was 5.05 g (98% yield). The infrared absorption spectrum of the polyimide, 1780 cm ^-1 (imide bond), 1727 cm ^-1 (imide bond), 1579cm ^-1 (triazine ring), 1377 cm ^-1 (imide bond), to ^1246cm -1 (C-F bond) Characteristic absorption was confirmed.

The logarithmic viscosity and molecular weight of this polyimide are shown below.
(1) Logarithmic viscosity: 0.65 dL / g (measured at 30 ° C. in N-methyl-2-pyrrolidone having a concentration of 0.5 g / dL)
(2) Molecular weight [measured by gel permeation chromatography using N-methyl-2-pyrrolidone solution containing lithium bromide (10 mmol / L) in terms of standard polystyrene]
Number average molecular weight (Mn): 83000
Weight average molecular weight (Mw): 219000
Molecular weight distribution (Mw / Mn): 2.64

This polyimide is also composed of N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidone (DMI), tetrahydrofuran (THF), 1,4-dioxane. , Dissolved in chloroform (CHCl ₃ ) at room temperature.

  This polyimide N-methyl-2-pyrrolidone solution is cast on a glass plate and dried under reduced pressure at 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to produce a yellow transparent polyimide film. did. From the result of the infrared absorption spectrum and elemental analysis of this film, it was confirmed that it was a polyimide film.

The characteristics of this polyimide film are shown below.
(1) Infrared absorption spectrum: 1780 cm ^-1 (imide bond), 1727 cm ^-1 (imide bond), 1377 cm ^-1 (imide bond)
(2) Elemental analysis _{[(C 91 H 45 F 35} N 8 O 9) Calculated as _n]:
Calculated C, 53.07%; H, 2.20%; N, 5.44%
Found C, 53.02%; H, 2.20%; N, 5.71%
(3) Glass transition temperature: 227 ° C. (differential scanning calorimetry)
(4) Thermal expansion coefficient: 82 ppm / ° C. (temperature range of 80 ° C. to 150 ° C.)
(5) Thermal decomposition temperature (thermogravimetric measurement)
5% weight loss temperature: 410 ° C. (in air), 405 ° C. (in nitrogen)
10% weight loss temperature: 435 ° C (in air), 430 ° C (in nitrogen)
(6) Tensile test Tensile strength: 71 MPa
Elongation at break: 14%
Tensile modulus: 3.7 MPa
(7) Water contact angle: 102 degrees

  This polyimide film was dissolved by heating in N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidone, and was insoluble in N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane and chloroform.

  To a 100 mL three-necked flask equipped with a nitrogen gas inlet tube, a condenser tube, and a Dean-Stark trap, 12.5 mL of distilled and purified N-methyl-2-pyrrolidone (NMP) and 2,2-bis [4- (4-aminophenoxy) ) Phenyl] hexafluoropropane (HFBAPP) 2.592 g (5 mmol) was added and dissolved with stirring. Next, this solution was cooled to 0 ° C., N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) (3.0 mL, 11 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes and further at room temperature for 30 minutes. N-silylated 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (silylated aromatic diamine compound S1) was derived. Thereafter, 0.806 g (2.5 mmol) of 3,4,3 ′, 4′-benzophenonetetracarboxylic dianhydride (BTDA) and 6- (4-perfluorononenyloxyanilino) -1,3,5- Add 1.718 g (2.5 mmol) of triazine-2,4-dichloride (monomer component) and stir for 4 hours at room temperature and 24 hours at 160 ° C. in a nitrogen gas stream to react with trimethylsilyl chloride and trimethyl. Silanol was removed from the system together with nitrogen gas.

After the reaction, a brown and viscous polymerization solution was poured into 400 mL of methanol to precipitate polyimide, and after filtration, dried under reduced pressure at 80 ° C. for 9 hours. The yield was 4.79 g (99% yield). According to the infrared absorption spectrum of polyimide, it is 1781 cm ⁻¹ (imide bond), 1728 cm ⁻¹ (imide bond), 1580 cm ⁻¹ (triazine ring), 1378 cm ⁻¹ (imide bond), 1247 cm ⁻¹ (CF bond). Characteristic absorption was confirmed.

The logarithmic viscosity of this polyimide is shown below.
(1) Logarithmic viscosity: 1.08 dL / g (measured at 30 ° C. in N-methyl-2-pyrrolidone having a concentration of 0.5 g / dL)
This polyimide is dissolved in N-methyl-2-pyrrolidone at room temperature, dissolved in 1,3-dimethyl-2-imidazolidone with heating, and dissolved in N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane and chloroform. Swelled.

  This polyimide N-methyl-2-pyrrolidone solution is cast on a glass plate and dried under reduced pressure at 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to produce a brown transparent polyimide film. did. The film was confirmed to be a polyimide film from the results of infrared absorption spectrum and elemental analysis.

The characteristics of this polyimide film are shown below.
(1) Infrared absorption spectrum: 1781 cm ⁻¹ (imide bond), 1728 cm ⁻¹ (imide bond), 1378 cm ⁻¹ (imide bond)
(2) Elemental analysis _{[(C 89 H 45 F 29} N 8 O 10) Calculated as _n]
Calculated C, 55.18%; H, 2.34%; N, 5.78%
Found C, 55.27%; H, 2.43%; N, 6.15%
(3) Glass transition temperature: 226 ° C. (differential scanning calorimetry)
(4) Thermal expansion coefficient: Measurement was impossible.
(5) Thermal decomposition temperature (thermogravimetric measurement)
5% weight loss temperature: 410 ° C. (in air), 410 ° C. (in nitrogen)
10% weight loss temperature: 435 ° C (in air), 430 ° C (in nitrogen)
(6) Contact angle of water: 104 degrees

  This polyimide film was dissolved in N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidone by heating, swollen in N, N-dimethylformamide, and insoluble in tetrahydrofuran, 1,4-dioxane and chloroform. It was.

  To a 100 mL three-necked flask equipped with a nitrogen gas inlet tube, a condenser tube, and a Dean-Stark trap, 12.5 mL of distilled and purified N-methyl-2-pyrrolidone (NMP) and 2,2-bis [4- (4-aminophenoxy) ) Phenyl] hexafluoropropane (HFBAPP) 2.592 g (5 mmol) was added and dissolved with stirring. Next, this solution was cooled to 0 ° C., N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) (3.0 mL, 11 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes and further at room temperature for 30 minutes. N-silylated 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (silylated aromatic diamine compound S1) was derived. Then, 0.74 g (2.5 mmol) of 4,4′-oxydiphthalic dianhydride (ODPA) and 6- (4-perfluorononenyloxyanilino) -1,3,5-triazine-2,4-dichloride (Monomer component) 1.718 g (2.5 mmol) was added, and the mixture was stirred and reacted at room temperature for 4 hours and further at 160 ° C. for 24 hours under a nitrogen stream. Removed.

After the reaction, the yellow and viscous polymerization solution was poured into 400 mL of methanol to precipitate polyimide, and after filtration, dried under reduced pressure at 80 ° C. for 9 hours. The yield was 4.72 g (98% yield). The infrared absorption spectrum of the polyimide, 1780 cm ^-1 (imide bond), 1727 cm ^-1 (imide bond), 1579cm ^-1 (triazine ring), 1377 cm ^-1 (imide bond), to ^1246cm -1 (C-F bond) Characteristic absorption was confirmed.

The logarithmic viscosity and molecular weight of this polyimide are shown below.
(1) Logarithmic viscosity: 0.70 dL / g (measured at 30 ° C. in N-methyl-2-pyrrolidone having a concentration of 0.5 g / dL)
(2) Molecular weight [measured by gel permeation chromatography using N-methyl-2-pyrrolidone solution containing lithium bromide (10 mmol / L) in terms of standard polystyrene]
Number average molecular weight (Mn): 106000
Weight average molecular weight (Mw): 217000
Molecular weight distribution (Mw / Mn): 2.05

  This polyimide was dissolved in N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, tetrahydrofuran, 1,4-dioxane and chloroform at room temperature.

  This polyimide N-methyl-2-pyrrolidone solution is cast on a glass plate and dried under reduced pressure at 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to produce a yellow transparent polyimide film. did. The film was confirmed to be a polyimide film from the results of infrared absorption spectrum and elemental analysis.

The characteristics of this polyimide film are shown below.
(1) Infrared absorption spectrum: 1780 cm ^-1 (imide bond), 1727 cm ^-1 (imide bond), 1377 cm ^-1 (imide bond)
(2) Elemental analysis _[calculated as _{(C 88 H 45 F 29 N} 8 O 10) n]:
Calculated C, 54.90%; H, 2.36%; N, 5.82%
Found C, 54.70%; H, 2.66%; N, 6.24%
(3) Glass transition temperature: 218 ° C. (differential scanning calorimetry)
(4) Thermal expansion coefficient: 71 ppm / ° C. (temperature range of 80 ° C. to 150 ° C.)
(5) Thermal decomposition temperature (thermogravimetric measurement)
5% weight loss temperature: 410 ° C. (in air), 410 ° C. (in nitrogen)
10% weight loss temperature: 440 ° C. (in air), 430 ° C. (in nitrogen)
(6) Tensile test Tensile strength: 71 MPa
Elongation at break: 3%
Tensile modulus: 3.7 MPa
(7) Water contact angle: 101 degrees

  This polyimide film swelled in N, N-dimethylformamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidone and was insoluble in tetrahydrofuran, 1,4-dioxane and chloroform.

  To a 100 mL three-necked flask equipped with a nitrogen gas inlet tube, a condenser tube, and a Dean-Stark trap, 12.5 mL of distilled and purified N-methyl-2-pyrrolidone (NMP) and 2,2-bis [4- (4-aminophenoxy) ) Phenyl] hexafluoropropane (HFBAPP) 2.592 g (5 mmol) was added and dissolved with stirring. Next, this solution was cooled to 0 ° C., N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) (3.0 mL, 11 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes and further at room temperature for 30 minutes. N-silylated 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (silylated aromatic diamine compound S1) was derived. Thereafter, 0.896 g (2.5 mmol) of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (DSDA) and 6- (4-perfluorononenyloxyanilino) -1,3,5 -Triazine-2,4-dichloride (monomer component) 1.718 g (2.5 mmol) was added, and the mixture was stirred at room temperature for 4 hours and further at 160 ° C. for 24 hours under a nitrogen gas stream. Trimethylsilanol was removed out of the system together with nitrogen gas.

After the reaction, a brown and viscous polymerization solution was poured into 400 mL of methanol to precipitate polyimide, and after filtration, dried under reduced pressure at 80 ° C. for 9 hours. The yield was 4.83 g (98% yield). According to the infrared absorption spectrum of polyimide, it is 1781 cm ⁻¹ (imide bond), 1728 cm ⁻¹ (imide bond), 1580 cm ⁻¹ (triazine ring), 1378 cm ⁻¹ (imide bond), 1247 cm ⁻¹ (CF bond). Characteristic absorption was confirmed.

The logarithmic viscosity and molecular weight of this polyimide are shown below.
(1) Logarithmic viscosity: 0.68 dL / g (measured at 30 ° C. in N-methyl-2-pyrrolidone having a concentration of 0.5 g / dL)
(2) Molecular weight [measured by gel permeation chromatography using N-methyl-2-pyrrolidone solution containing lithium bromide (10 mmol / L) in terms of standard polystyrene]
Number average molecular weight (Mn): 69000
Weight average molecular weight (Mw): 150,000
Molecular weight distribution (Mw / Mn): 2.17

  This polyimide was dissolved in N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone, tetrahydrofuran, 1,4-dioxane and chloroform at room temperature.

  This polyimide N-methyl-2-pyrrolidone solution is cast on a glass plate and dried under reduced pressure at 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to produce a brown transparent polyimide film. did. The film was confirmed to be a polyimide film from the results of infrared absorption spectrum and elemental analysis.

The characteristics of this polyimide film are shown below.
(1) Infrared absorption spectrum: 1781 cm ⁻¹ (imide bond), 1728 cm ⁻¹ (imide bond), 1378 cm ⁻¹ (imide bond)
(2) Elemental analysis [calculated as (C ₈₈ H ₄₅ F ₂₉ N ₈ O ₁₁ S) _n ]:
Calculated C, 53.56%; H, 2.30%; N, 5.68%
Found C, 53.81%; H, 2.35%; N, 5.92%
(3) Glass transition temperature: 229 ° C. (differential scanning calorimetry)
(4) Thermal expansion coefficient: 80 ppm / ° C. (temperature range of 80 ° C. to 160 ° C.)
(5) Thermal decomposition temperature (thermogravimetric measurement)
5% weight loss temperature: 410 ° C. (in air), 410 ° C. (in nitrogen)
10% weight loss temperature: 435 ° C (in air), 430 ° C (in nitrogen)
(6) Tensile test Tensile strength: 80 MPa
Elongation at break: 6%
Tensile modulus: 3.5 MPa
(7) Water contact angle: 102 degrees

  This polyimide film was dissolved by heating in N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidone, and was insoluble in N, N-dimethylformamide, tetrahydrofuran, 1,4-dioxane and chloroform.

  In a 100 mL three-necked flask equipped with a nitrogen gas inlet tube, a condenser tube, and a Dean-Stark trap, 12.5 mL of distilled and purified N-methyl-2-pyrrolidone (NMP) and 4,4′-oxydianiline (ODA) 001 g (5 mmol) was added and dissolved while stirring. Next, this solution was cooled to 0 ° C., N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) (3.0 mL, 11 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes and further at room temperature for 30 minutes. N-silylated 4,4'-oxydianiline (silylated aromatic diamine compound S2) was derived. Then, 1.111 g (2.5 mmol) of 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) and 6- (4-perfluorononenyloxyanilino) -1,3,5-triazine 1.718 g (2.5 mmol) of 2,4-dichloride (monomer component) was added, and the mixture was reacted by stirring at room temperature for 4 hours and further at 160 ° C. for 24 hours under a nitrogen gas stream. By-product trimethylsilyl chloride and trimethylsilanol were reacted. Was removed out of the system together with nitrogen gas.

After the reaction, the yellow and viscous polymerization solution was poured into 400 mL of methanol to precipitate polyimide, and after filtration, dried under reduced pressure at 80 ° C. for 9 hours. The yield was 3.49 g (98% yield). The infrared absorption spectrum of the polyimide, 1780 cm ^-1 (imide bond), 1727 cm ^-1 (imide bond), 1579cm ^-1 (triazine ring), 1377 cm ^-1 (imide bond), to ^1246cm -1 (C-F bond) Characteristic absorption was confirmed.

The logarithmic viscosity and molecular weight of this polyimide are shown below.
(1) Logarithmic viscosity: 0.65 dL / g (measured at 30 ° C. in N-methyl-2-pyrrolidone having a concentration of 0.5 g / dL)
(2) Molecular weight [measured by gel permeation chromatography using a N-methyl-2-pyrrolidone solution containing lithium bromide (10 mmol / L) in terms of standard polystyrene]
Number average molecular weight (Mn): 94000
Weight average molecular weight (Mw): 186000
Molecular weight distribution 8 Mw / Mn): 1.98
This polyimide is dissolved in N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone at room temperature, dissolved in tetrahydrofuran and 1,4-dioxane, and dissolved in chloroform. Was insoluble.

  This polyimide N-methyl-2-pyrrolidone solution is cast on a glass plate and dried under reduced pressure at 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to produce a yellow transparent polyimide film. did. The film was confirmed to be a polyimide film from the results of infrared absorption spectrum and elemental analysis.

The characteristics of this polyimide film are shown below.
(1) Infrared absorption spectrum: 1780 cm ^-1 (imide bond), 1727 cm ^-1 (imide bond), 1377 cm ^-1 (imide bond)
(2) Elemental analysis [calculated as (C ₆₁ H ₂₉ F ₂₃ N ₈ O ₇ ) _n ]:
Calculated C, 51.49%; H, 2.05%; N, 7.88%
Found C, 51.27%; H, 2.15%; N, 8.08%
(3) Glass transition temperature: 255 ° C. (differential scanning calorimetry)
(4) Thermal expansion coefficient: 84 ppm / ° C. (temperature range of 80 ° C. to 150 ° C.)
(5) Thermal decomposition temperature (thermogravimetric measurement)
5% weight loss temperature: 420 ° C. (in air), 410 ° C. (in nitrogen)
10% weight loss temperature: 440 ° C. (in air), 430 ° C. (in nitrogen)
(6) Tensile test Tensile strength: 97 MPa
Elongation at break: 5%
Tensile modulus: 4.2 MPa
(7) Water contact angle: 104 degrees

  This polyimide film was dissolved by heating in N-methyl-2-pyrrolidone, swollen in N, N-dimethylformamide and 1,3-dimethyl-2-imidazolidone, and insoluble in tetrahydrofuran, 1,4-dioxane and chloroform. It was.

  In a 100 mL three-necked flask equipped with a nitrogen gas inlet tube, a condenser tube, and a Dean-Stark trap, 12.5 mL of distilled and purified N-methyl-2-pyrrolidone (NMP) and 4,4′-oxydianiline (ODA) 001 g (5 mmol) was added and dissolved while stirring. Next, this solution was cooled to 0 ° C., N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) (3.0 mL, 11 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes and further at room temperature for 30 minutes. N-silylated 4,4'-oxydianiline (silylated aromatic diamine compound S2) was derived. Then, 0.74 g (2.5 mmol) of 4,4′-oxydiphthalic dianhydride (ODPA) and 6- (4-perfluorononenyloxyanilino) -1,3,5-triazine-2,4-dichloride (Monomer component) 1.718 g (2.5 mmol) was added, and the mixture was stirred and reacted at room temperature for 4 hours and further at 160 ° C. for 24 hours under a nitrogen stream. Removed.

After the reaction, the yellow and viscous polymerization solution was poured into 400 mL of methanol to precipitate polyimide, and after filtration, dried under reduced pressure at 80 ° C. for 9 hours. The yield was 3.16 g (98% yield). The infrared absorption spectrum of the polyimide, 1780 cm ^-1 (imide bond), 1727 cm ^-1 (imide bond), 1579cm ^-1 (triazine ring), 1377 cm ^-1 (imide bond), to ^1246cm -1 (C-F bond) Characteristic absorption was confirmed.

The logarithmic viscosity and molecular weight of this polyimide are shown below.
(1) Logarithmic viscosity: 0.63 dL / g (measured at 30 ° C. in N-methyl-2-pyrrolidone having a concentration of 0.5 g / dL)
(2) Molecular weight [measured by gel permeation chromatography using N-methyl-2-pyrrolidone solution containing lithium bromide (10 mmol / L) in terms of standard polystyrene]
Number average molecular weight (Mn): 101000
Weight average molecular weight (Mw): 216000
Molecular weight distribution (Mw / Mn): 2.14

  This polyimide is dissolved in N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidone at room temperature, dissolved in tetrahydrofuran and 1,4-dioxane, and dissolved in chloroform. Was insoluble.

  This polyimide N-methyl-2-pyrrolidone solution is cast on a glass plate and dried under reduced pressure at 100 ° C for 1 hour, 200 ° C for 1 hour, and 300 ° C for 1 hour to produce a yellow transparent polyimide film. did. The film was confirmed to be a polyimide film from the results of infrared absorption spectrum and elemental analysis.

The characteristics of this polyimide film are shown below.
(1) Infrared absorption spectrum: 1780 cm ^-1 (imide bond), 1727 cm ^-1 (imide bond), 1377 cm ^-1 (imide bond)
(2) Elemental analysis [(C ₅₈ H ₂₉ F ₁₇ N ₈ O ₈ ) calculated as _n ]:
Calculated C, 54.05%; H, 2.27%; N, 8.69%
Found C, 53.79%; H, 2.47%; N, 8.88%
(3) Glass transition temperature: 243 ° C. (differential scanning calorimetry)
(4) Thermal expansion coefficient: 80 ppm / ° C. (temperature range of 80 ° C. to 150 ° C.)
(5) Thermal decomposition temperature (thermogravimetric measurement)
5% weight loss temperature: 420 ° C. (in air), 410 ° C. (in nitrogen)
10% weight loss temperature: 440 ° C (in air), 430 ° C (in nitrogen)
(6) Tensile test Tensile strength: 93 MPa
Elongation at break: 5%
Tensile modulus: 4.3 MPa
(7) Water contact angle: 103 degrees

  This polyimide film swelled in N, N-dimethylformamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidone and was insoluble in tetrahydrofuran, 1,4-dioxane and chloroform.

In Example 8 of the present invention, the water-repellent properties of the coating film itself when used as a primer or binder (undercoat layer or adhesive) for the fluorine-containing polyimide resins produced in Examples 2 and 4 of the present invention, The heat resistance, durability and chemical resistance were investigated. The specimens of the examples of the present invention are two types of fluorine-containing polyimide resins shown in Table 5. These two types of fluorine-containing polyimide resins are N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidone (DMI), tetrahydrofuran as described above. (THF), 1,4-dioxane, chloroform (CHCl ₃ ) dissolved at room temperature.

As an aromatic tetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was used in Example 2, and 4,4′-oxydiphthalic dianhydride was used in Example 4. (ODPA) is used. In the production of these two types of fluorine-containing polyimide resins, HFBAPP was used as the aromatic diamine, and N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) was used as the silylating agent for HFBAPP. The monomer component added to the silylated aromatic diamine together with the aromatic tetracarboxylic dianhydride is 6- (4-perfluorononenyloxyanilino) -1,3,5-triazine-2,4-dichloride. Was used. Further, the fluorine-containing polyimide resin produced in Example 2 is abbreviated as HFBAPP / 6FDA, and the fluorine-containing polyimide resin produced in Example 4 is abbreviated as HFBAPP / ODPA. The basic physical properties of these two resins, glass transition temperature Tg (DSC: by differential scanning calorimetry), 5% weight loss temperature Td ₅ (in air or nitrogen gas), linear expansion coefficient CTE As already shown in Examples 2 and 4, it is reproduced in Table 5.

  Table 6 shows the construction conditions. A stainless steel plate SUS304 was used as the substrate to be coated, the SUS304 plate was blasted, the two types of fluorine-containing polyimide resin films were placed thereon, and heated under the conditions shown in Table 6. The substrate to be coated may be any material, for example, metal or ceramic. In the case of a metal, for example, various steel materials including stainless steel, aluminum and the like can be targeted.

  A contact angle of water, a cross-cut test (JISK6894), and a drawing test (JISK6894) were performed using the above test specimens. The results were as shown in Table 7. In addition, the comparative example shown in Table 7 is three types, a polyimide dispersion, a low temperature curing type polyimide, and a silicone modified polyimide.

  According to Table 7, it was found that the two types of fluorine-containing polyimide resins of the examples of the present invention had a contact angle with water of 90 ° or more and higher water repellency than the silicone-modified polyimide resin. It can also be seen that the surface energy is clearly lower than that of polyimide dispersion and low-temperature curing type polyimide.

  In addition, each of the inventive examples was able to obtain 100/100 (number of squares in close contact after the test / number of squares with cuts (JIS K6894)) in the cross-cut test. In addition, in the examples of the present invention, in the drawing test, it was possible to obtain 5 points which are the highest points specified in the above JISK6894. On the other hand, in the polyimide dispersion of the comparative example, in the cross-cut test and the drawing test, a result comparable to that of the present invention example was obtained, but in the low-temperature curing type polyimide, the cross-cut test result is 0/100, In addition, the drawing test result is 3 points, which is greatly deteriorated. As for the silicone-modified polyimide, results similar to those of the examples of the present invention were obtained in both the cross-cut test and the drawing test.

  Table 8 shows the results of the chemical resistance test. As the chemicals, NMP (N-methyl-2-pyrrolidone) and 15% by volume sodium hypochlorite aqueous solution (Kitchen Hiter) were used, and after immersing the test specimens in these chemicals, a cross-cut test (JISK6894) was performed.

  According to Table 8, the polyimide dispersion of the comparative example was able to obtain a 100/100 good result in the cross cut test after NMP immersion, but it was completely in the 15 volume% sodium hypochlorite aqueous solution. Dissolved. Moreover, in the low temperature curing type polyimide, severe swelling occurred in the NMP immersion, and softening occurred slightly in the 15 volume% sodium hypochlorite aqueous solution immersion, and the cross-cut test was impossible after any chemical solution immersion. On the other hand, in the example of the present invention, decoloration occurred slightly in HFBAPP / ODPA, and in HFBAPP / 6FDA, several blisters were sometimes observed after being immersed in a 15% by volume sodium hypochlorite aqueous solution, but there was no problem. . Subsequent cross-cut testing demonstrated that both of the inventive examples had sufficient peel resistance against NMP and 15% by volume sodium hypochlorite aqueous solution.

  Since the above HFBAPP / ODPA and HFBAPP / 6FDA contain a fluorine atom, the adhesiveness with other fluororesins is high. Therefore, according to Example 8 of the present invention, it was verified that the above-mentioned two types of fluorine-containing polyimide resin films are very effective as a base treatment layer for fluororesin coating on a substrate to be coated such as metal. It was.

  In Example 9 of the present invention, an example in which a SUS304 stainless steel plate is coated with a fluororesin using a primer containing the above-described fluorine-containing polyimide resin and fluororesin will be described. First, the primer containing said fluorine-containing polyimide resin and fluororesin was apply | coated to the SUS304 stainless steel plate by electrostatic powder coating. As the fluororesin mixed with the fluoropolyimide resin, PFA (perfluoroalkoxy) resin ACX-30 (manufactured by Daikin Industries, Ltd.) was used. Next, the step of firing the fluororesin layer was repeated several times by a known method to obtain a film having a thickness of 603 μm to 627 μm. A composite plate in which a stainless steel plate is coated with a fluororesin as described above is called a panel.

  Table 9 shows the results of measuring the adhesion of the fluororesin coating layer in the panel. According to Table 9, when HFBAPP / ODPA fluorine-containing polyimide resin was used as a primer, sufficient adhesion could not be obtained at any compounding ratio. On the other hand, when the fluorine-containing polyimide resin of HFBAPP / 6FDA was used as the primer, sufficient initial adhesion could be obtained at any compounding ratio. The film rupture indicates film strength> adhesive strength. In the above case, the film rupture is determined to be 1 in the range of HBAPP / 6FDA in the range of 4: 6 to 9: 1. .76kgf / 5mm or more.

  The panel was exposed to a steam sterilizer at a temperature of 143 ° C./60 min in order to investigate the blending ratio of the primer for obtaining higher adhesion (ratio of fluororesin to the above-mentioned fluorine-containing polyimide resin). As a result, it was found that when the ACX-30: (HFBAPP / 6FDA) has a blending ratio of 6: 4, high adhesion is maintained. As an example of the present invention, the penetration test into the drug was conducted at the above-mentioned mixing ratio of 6: 4. Using a TG / DTA (differential calorific value simultaneous measurement device), the test specimen prepared under the same construction conditions as the test specimen (panel) for measuring the adhesion force shown in Table 9 was measured, and the weight was reduced. And the behavior of calorie change was investigated. According to the above TG / DTA measurement results, the weight continues to decrease in a small amount, but no rapid weight loss is observed, heat resistance is sufficient, and initial adhesion is sufficient. Advanced. For the comparative example, a mixed system primer of PPS (polyphenylene sulfide) resin and PFA resin ACX-30 was selected. As the PPS resin, W-220F (manufactured by Kureha Chemical Industry Co., Ltd.) was used.

  The penetration test was performed using a lining tester (manufactured by Yamazaki Seiki Laboratory Co., Ltd.) generally used in a corrosion resistance test for resin lining. In this lining tester, when testing the chemical resistance and penetration resistance of the lining film on the table, conditions such as chemical solution, temperature, temperature gradient, etc. assuming the use conditions of the actual machine can be set, and over time related to corrosion resistance deterioration The degree of permeation and diffusion of chemicals and water can be examined. A panel coated with fluororesin under the same construction conditions as the panel for which adhesion was measured was used as a test specimen. The panel is attached to both ends of a heat-resistant cylindrical glass cell horizontally filled with 60 to 70% of the drug so as to close the cylindrical cell, and exposed to the liquid phase and gas phase of the drug at a predetermined temperature. The test time was passed.

  According to Table 10 showing the results of the penetration test, in Example A of the present invention, no abnormality was observed up to 128.5 h, and a plurality of fine blisters were observed in the liquid phase immersion portion when 216 h10 min had elapsed. On the other hand, in Comparative Example B, blisters having a diameter of about 3 mm were generated in both gas-liquid phases at 128.5 h. Moreover, when 216h10min passed, these blisters became large and generation | occurrence | production of a new blister was recognized.

  FIG. 1 is a view showing a state of the panel of Example A of the present invention after the penetration test and an adhesion distribution by a destructive inspection in that state. The panel 1 is attached to a cylindrical cell of the penetrating test apparatus with a stopper such as a screw inserted through the panel mounting hole 2 and used for the test. A circular cylindrical cell is used for the gas phase and liquid phase of the drug. The contact was made inside the contact part 3. In FIG. 1, a blister having a diameter of about 2 mm is generated at a portion in contact with the liquid phase, but the adhesion force disappears at one location, and the adhesion strength at 0.07 kgf / 5 mm or more is maintained at the other location. It was. Moreover, FIG. 2 is a figure which shows the state after the penetration test of the panel of the comparative example B, and adhesion distribution by the destructive inspection in the state. The meaning of the reference numerals is the same as in FIG. According to FIG. 2, a large blister having a diameter of about 7 mm was generated in a portion in contact with the liquid phase or the gas phase, and the adhesion was lost in many places.

  In the drug penetration test of a primer containing hexavalent chromium that tends to be abolished due to its toxicity, the primer in Example A of the present invention is considered in consideration that blisters having a diameter of about 2 mm are generated at about 200 to 250 hours. It has great potential as an alternative to hexavalent chromium-containing primers.

  The embodiment disclosed this time should be considered as illustrative in all points and not restrictive. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

  The fluorine-containing polyimide resin according to the present invention is a primer or binder having heat resistance, chemical resistance, water repellency, mechanical strength, durability, and adhesiveness when a coated substrate is coated with a fluorine resin or the like. Since it can be used for the treatment layer, it is expected to contribute greatly in this field.

It is a figure which shows the state after the penetration test of the panel of the example A of this invention, and adhesion distribution by the destructive inspection in the state. It is a figure which shows the state after the penetration test of the panel of the comparative example B, and adhesion distribution by the destructive inspection in the state.

Explanation of symbols

  1 panel, 2 panel mounting hole, 3 cylindrical cell contact part.

Claims (5)

General formula (1)

(In the formula, R represents a perfluoroalkenyl group or a perfluoroalkyl group, Ar represents a divalent aromatic residue, Ar ′ represents a tetravalent aromatic residue, and n represents an integer of 10 to 200. )), A fluorine-containing polyimide resin. One or two or more of the aromatic diamines represented by the general formula (2) represented by H ₂ N—Ar—NH ₂ (2) (Ar is the same as described above) are used as one or more silylating agents. Silylated compounds and general formula (3)

(Wherein X represents a halogen atom and R is the same as above), one or more triazine dihalides represented by the general formula (4)

(In the formula, Ar ′ is the same as described above) is reacted with one or more of the aromatic tetracarboxylic dianhydrides represented by the general formula (1)

(Wherein R, Ar, Ar ′, n are the same as above), a method for producing a fluorine-containing polyimide resin. In the general formula (2), one or two or more of aromatic diamines represented by H ₂ N—Ar—NH ₂ (2) are silylated with one or two or more silylating agents, and the general formula (3)

(Wherein X and R are the same as defined above) and one or more triazine dihalides represented by the general formula (4)

(In the formula, Ar ′ is the same as described above) A fluorine-containing polyimide resin obtained by reacting with one or two or more of aromatic tetracarboxylic dianhydrides.   A primer comprising one or more of the fluorine-containing polyimide resin according to claim 1 or 3 or the fluorine-containing polyimide resin produced by the production method according to claim 2 and a fluorine resin.   The coated substrate is coated with one or more of the fluorine-containing polyimide resin according to claim 1 or 3 or the fluorine-containing polyimide resin produced by the production method according to claim 2 as a binder. Resin coating method.

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