JP2007091855A - Film manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film manufacturing process which reduces defects such as scratches and streaks of a film obtained and yields a polyarylene film with an excellent appearance in obtaining the film from a composition containing a polyarylene having sulfonic acid groups and an organic solvent by casting. <P>SOLUTION: The film manufacturing process involves a step (1) to form a coated film by coating a composition containing a polyarylene having sulfonic acid groups and an organic solvent on a substrate and drying the composition and a step (2) to reduce the content of the remaining organic solvent in the coated film. The sulfonic acid equivalent of the polyarylene is ≥0.3 meq/g. The content of the remaining organic solvent in 100 pts.wt. of the coated film obtained in the step (2) is ≤0.5 pt.wt. The peel strength between the coated film obtained in the step (2) and the substrate is 0.05-2 N/25 mm width at a pulling rate of 0.7 m/min in the 180° peel test. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a polyarylene film, and more specifically, an electrolyte for a primary battery, an electrolyte for a secondary battery, a polymer solid electrolyte for a fuel cell, a display element, various sensors, a signal transmission medium, a solid capacitor, an ion The present invention relates to a method for producing a polyarylene-based film useful as a proton conductive membrane used for an exchange membrane or the like.

  The sulfonated aromatic polymer is usually formed into a film and used as a proton conductive membrane of a fuel cell. Examples of a method for forming a conductive film using a sulfonated aromatic polymer include a method in which a sulfonated aromatic polymer is dissolved in an organic solvent and formed into a film by a casting method (for example, Patent Documents). 1).

  However, when a sulfonated aromatic polymer is cast on a surface-treated substrate and dried, a film composed of the sulfonated aromatic polymer is formed from the substrate due to the interaction with the surface treatment agent on the substrate. It becomes difficult to peel off. Thus, when peeling of the film from a base | substrate becomes difficult, it will have abnormality in the external appearance of a film and defects, such as a peeling flaw and a stripe, may generate | occur | produce. In particular, in the case of polyarylene having a sulfonic acid group having a high sulfonic acid equivalent (for example, 0.3 meq / g or more) and useful as a proton conductive membrane, the mutual treatment between the sulfonic acid group and the surface treatment agent applied to the substrate. The action tends to occur, and the above-mentioned peeling scratches and streaks may occur.

  Here, when used for electrical / electronic materials such as proton conducting membranes, an important characteristic required for a film is a fuel barrier property that gas fuel or liquid fuel is not allowed to pass through the opposite side of the film. When the above film having peeling scratches and streaks is used as a polymer solid electrolyte for a fuel cell for a long time, the peeling scratches and streaks become serious problems such as gas leaks and fuel leaks. .

  Further, in the case of polyarylene having a sulfonic acid group, the drying temperature is high because the organic solvent for casting has a relatively high boiling point. When the drying is performed at a high temperature, the substrate is thermally contracted, and thus the film appearance abnormality such as streaks and wrinkles tends to occur in the film. These abnormal appearances also become a serious problem as described above.

When a film made of a sulfonated aromatic polymer is used for an electric / electronic material such as a proton conducting membrane, it is necessary to transfer the film surface by pressing an electrode or the like. Here, in the film obtained by the casting method, the surface roughness of the surface touching the substrate appears as a result of the surface roughness of the substrate being transferred. Therefore, in the process of transferring the electrode or the like to the film surface, if the surface roughness of the film is large, the electrode cannot be uniformly transferred and can no longer be used as a polymer solid electrolyte for fuel cells. .
JP 2005-171027 A

  An object of the present invention is to reduce defects such as peeling scratches and streaks of the obtained film when a film is obtained by a casting method from a composition containing a polyarylene having a sulfonic acid group and an organic solvent, and has an excellent appearance. It is providing the film manufacturing method from which a polyarylene-type film is obtained.

  The present inventors diligently studied to solve the above problems. As a result, in the film formation by the casting method of polyarylene containing sulfonic acid groups, the film has excellent appearance by casting on a substrate that has not been surface-treated and reducing the amount of solvent remaining in the coating film. It was found that can be obtained.

  That is, the film manufacturing method according to the present invention includes a step (1) of forming a coating film by applying a polyarylene-based composition containing a polyarylene containing a sulfonic acid group and an organic solvent to a substrate and drying it. And the step (2) of reducing the content of the organic solvent remaining in the coating film, the sulfonic acid equivalent of the polyarylene is 0.3 meq / g or more, and is obtained in the step (2). The content of the organic solvent remaining in 100 parts by weight of the coated film is 0.5 parts by weight or less, and the peel strength between the coated film obtained in the step (2) and the substrate is a 180 ° peel test. It is characterized by being in the range of 0.05 to 2 N / width 25 mm under the condition of a pulling speed of 0.7 m / min.

  The polyarylene preferably includes a structural unit represented by the following general formula (A) and a structural unit represented by the following general formula (B).

In the formula (A), Y represents —CO—, —SO ₂ —, —SO—, —CONH—, —COO—, —
(CF ₂ ) _i — (i represents an integer of 1 to 10) or —C (CF ₃ ) ₂ —, Z is independently a direct bond, — (CH ₂ ) _j — (j is 1 to Represents an integer of 10.), —C (CH ₃ ) ₂ —, —O— or —S—, and Ar represents —SO ₃ H, —O (CH ₂ ) _p SO ₃ H or —O (CF _{2) p} SO ₃ H _(p represents an aromatic group having a substituent represented by indicating.) an integer of 1 to 12, m represents an integer of 0, n is an integer of 0 K represents an integer of 1 to 4.

In formula (B), A and D are each independently a direct bond, —CO—, —SO ₂ —, —SO
-, - CONH -, - COO -, - (CF 2) i -, (i is an integer of _{1~10.) - (CH 2)} j -, (j is an integer of 1 to 10.) —CR ′ ₂ — (R ′ is an aliphatic hydrocarbon group,
An aromatic hydrocarbon group or a halogenated hydrocarbon group is shown. ), A cyclohexylidene group, a fluorenylidene group, —O— or —S—, B independently represents an oxygen atom or a sulfur atom, and R ^{1 to} R ¹⁶ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. Represents a partially or fully halogenated alkyl group, allyl group, aryl group, nitro group or nitrile group, s and t each represents an integer of 0 to 4, and r is 0 or 1 or more Indicates an integer.

  The substrate is polyethylene terephthalate, the center line average roughness of the surface of the substrate is 0.02 μm or less, and the thermal shrinkage of the substrate is 0.9% in the unwinding direction of the substrate. And preferably 0.2% or less in the width direction of the substrate.

  According to the present invention, defects such as peeling scratches and streaks are reduced, and a polyarylene film having an excellent appearance can be obtained. Therefore, the polyarylene-based film (proton conductive membrane) obtained from the present invention is used as an electrolyte for primary batteries, an electrolyte for secondary batteries, a polymer solid electrolyte for fuel cells, a display element, various sensors, a signal transmission medium, a solid capacitor, When used as a conductive membrane such as an ion exchange membrane, it exhibits high pronton conductivity over a wide temperature range and can be used for a long time without impairing film properties.

Hereinafter, the film manufacturing method according to the present invention will be described in detail.
The method for producing a film according to the present invention comprises applying a polyarylene-based composition containing a polyarylene having a sulfonic acid group (hereinafter also referred to as “sulfonated polyarylene”) and an organic solvent to a substrate and drying. The process (1) which forms a film | membrane, and the process (2) which reduces content of the organic solvent which remains in this coating film are included.

[Sulfonated polyarylene]
The sulfonated polyarylene used in the present invention is not particularly limited, but is also a structural unit having a sulfonic acid group represented by the following general formula (A) (hereinafter referred to as “sulfonic acid unit” or “structural unit (A)”). And a structural unit having no sulfonic acid group represented by the following general formula (B) (hereinafter also referred to as “hydrophobic unit” or “structural unit (B)”) A polymer represented by the formula (C) is preferable.

  <Sulphonic acid unit>

In the above formula (A), Y represents —CO—, —SO ₂ —, —SO—, —CONH—, —COO—.
_{, - (CF 2) i -} (i is an integer from 1 to 10.) Or -C (CF _{3) 2} - shows a. Of these, —CO— and —SO ₂ — are preferable.

Z independently represents a direct bond, — (CH ₂ ) _j — (j represents an integer of 1 to 10), —C (CH ₃ ) ₂ —, —O— or —S—. Among these, a direct bond and —O— are preferable.

Ar is —SO ₃ H, —O (CH ₂ ) _p SO ₃ H or —O (CF ₂ ) _p SO ₃ H (p is 1 to
An integer of 12 is shown. The aromatic group which has a substituent represented by this is shown. Examples of the aromatic group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and the like. In these, a phenyl group and a naphthyl group are preferable. Ar represents —SO ₃ H;
It is necessary to have at least one substituent represented by —O (CH ₂ ) _p SO ₃ H or —O (CF ₂ ) _p SO ₃ H, and two in the case of a naphthyl group It is preferable to have the above.

m is an integer of 0 to 10, preferably 0 to 2, n is an integer of 0 to 10, preferably 0 to 2, and k is an integer of 1 to 4.
As a preferred structure of the structural unit (A), in the above formula (A),
(1) a structure in which m = 0, n = 0, Y is —CO—, and Ar is a phenyl group having —SO ₃ H as a substituent;
(2) a structure in which m = 1, n = 0, Y is —CO—, Z is —O—, and Ar is a phenyl group having —SO ₃ H as a substituent;
(3) A structure in which m = 1, n = 1, k = 1, Y is —CO—, Z is —O—, and Ar is a phenyl group having —SO ₃ H as a substituent;
(4) m = 1, n = 0, Y is —CO—, and Ar is two substituents —SO _3.
A structure which is a naphthyl group having H,
(5) m = 1, n = 0, Y is —CO—, Z is —O—, and Ar is a phenyl group having —O (CH ₂ ) ₄ SO ₃ H as a substituent. Examples include structures.

  <Hydrophobic unit>

In the above formula (B), A and D are each independently a direct bond, —CO—, —SO ₂ —, —
SO—, —CONH—, —COO—, — (CF ₂ ) _i — (i represents an integer of 1 to 10), — (CH ₂ ) _j — (j represents an integer of 1 to 10) , -CR _'2 -, showing cyclohexylidene group, a fluorenylidene group, -O- or -S-. Among these, a direct bond, —CO—, —SO ₂ —, —CR ′ ₂ —, a cyclohexylidene group, a fluorenylidene group, and —O— are preferable. R ′ represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated hydrocarbon group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, A propyl group, an octyl group, a decyl group, an octadecyl group, a phenyl group, a trifluoromethyl group, etc. are mentioned.

B independently represents an oxygen atom or a sulfur atom, preferably an oxygen atom.
R ^{1 to} R ¹⁶ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group, an allyl group, an aryl group, a nitro group or a nitrile group, which is partially or wholly halogenated.

Examples of the alkyl group in R ^{1 to} R ¹⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a cyclohexyl group, and an octyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Examples of the allyl group include a propenyl group. Examples of the aryl group include a phenyl group and a pentafluorophenyl group.

s and t each represent an integer of 0 to 4. r shows 0 or an integer greater than or equal to 1, and an upper limit is 100 normally, Preferably it is 1-80.
As a preferable structure of the structural unit (B), in the above formula (B),
(1) s = 1, t = 1, A is —CR ′ ₂ —, a cyclohexylidene group or a fluorenylidene group, B is an oxygen atom, and D is —CO— or —SO ₂ —. , R ^{1 to} R ¹⁶ are hydrogen atoms or fluorine atoms,
(2) a structure in which s = 1, t = 0, B is an oxygen atom, D is —CO— or —SO ₂ —, and R ^{1 to} R ¹⁶ are hydrogen atoms or fluorine atoms,
(3) s = 0, t = 1, A is —CR ′ ₂ —, a cyclohexylidene group or a fluorenylidene group, B is an oxygen atom, and R ^{1 to} R ¹⁶ are a hydrogen atom, a fluorine atom or Examples thereof include a structure that is a nitrile group.

  <Polymer structure>

In the above formula (C), A, B, D, Y, Z, Ar, k, m, n, r, s, t and R ^{1 to} R ¹⁶ are defined in the above formulas (A) and (B). Where x and y are x + y = 10
The molar ratio in the case of 0 mol% is shown.

  The sulfonated polyarylene particularly preferably used in the present invention contains the structural unit (A), that is, the unit x, in a proportion of 0.5 to 100 mol%, preferably 10 to 99.999 mol%, The unit (B), that is, the unit of y is contained in a proportion of 99.5 to 0 mol%, preferably 90 to 0.001 mol%.

<Method for producing polymer>
Examples of the method for producing the sulfonated polyarylene include the following methods A, B, and C.

  (Method A) For example, by the method described in JP-A No. 2004-137444, a monomer having a sulfonate group that can be the structural unit (A) and a monomer or oligomer that can be the structural unit (B) A method of polymerizing to produce a polyarylene having a sulfonic acid ester group, and deesterifying the sulfonic acid ester group to convert it into a sulfonic acid group.

  (Method B) For example, in the method described in JP-A-2001-342241, a monomer having a skeleton represented by the above formula (A) but not having a sulfonic acid group or a sulfonic acid ester group, and the above structural unit (B) A method in which a monomer or an oligomer that can be used is copolymerized, and the resulting copolymer is sulfonated using a sulfonating agent.

(Method C) When Ar in the above formula (A) is an aromatic group having a substituent represented by —O (CH ₂ ) _p SO ₃ H or —O (CF ₂ ) _p SO ₃ H Is, for example, copolymerized a precursor monomer that can be the structural unit (A) and a monomer or oligomer that can be the structural unit (B) by the method described in JP-A-2005-60625, A method of introducing an alkyl sulfonic acid or a fluorine-substituted alkyl sulfonic acid.

  Examples of the monomer having a sulfonate group that can be the structural unit (A) that can be used in the method A include, for example, JP-A Nos. 2004-137444, 2004-345997, and 2004-346163. Examples thereof include sulfonic acid esters described in Japanese Patent Publication No. Gazette.

  Examples of the monomer having no sulfonic acid group and sulfonic acid ester group that can be the structural unit (A) that can be used in the above-mentioned method B include, for example, JP-A Nos. 2001-342241 and 2002-293889. Mention may be made of the dihalides described.

  Examples of the precursor monomer that can be the structural unit (A) that can be used in the method C include dihalides described in JP-A-2005-36125.

In addition, as a monomer or oligomer that can be the structural unit (B) used in any method,
When r = 0, for example, 4,4′-dichlorobenzophenone, 4,4′-dichlorobenzanilide, 2,2-bis (4-chlorophenyl) difluoromethane, 2,2-bis (4-chlorophenyl) -1 , 1,1,3,3,3-hexafluoropropane, 4-chlorobenzoic acid-4-chlorophenyl ester, bis (4-chlorophenyl) sulfoxide, bis (4-chlorophenyl) sulfone, 2,6-dichlorobenzonitrile, etc. Is mentioned. Among these compounds, compounds in which a chlorine atom is replaced with a bromine atom or an iodine atom can also be used.

In the case of r = 1, for example, compounds described in JP-A-2003-113136 can be exemplified.
In the case of r ≧ 2, for example, JP 2004-137444 A, JP 2004-244517 A, JP 2004-346164 A, JP 2005-112985 A, Japanese Patent Application No. 2004-211739, and Japanese Patent Application No. 2004. And compounds described in No. -211740.

  In order to obtain a polyarylene having a sulfonic acid group, first, a monomer that can be the structural unit (A) and a monomer or oligomer that can be the structural unit (B) are copolymerized in the presence of a catalyst. It is necessary to obtain body polyarylene. The catalyst used in carrying out the copolymerization is a catalyst system containing a transition metal compound, and this catalyst system is (i) a compound that becomes a transition metal salt and a ligand, or a ligand is coordinated. In addition, a transition metal complex (including a copper salt) and (ii) a reducing agent may be essential components, and a “salt” may be added to increase the polymerization rate. Specific examples of these catalyst components, the use ratio of each component, the polymerization conditions such as the reaction solvent, concentration, temperature, time, etc. can employ the conditions described in JP-A-2001-342241, for example. .

  The sulfonated polyarylene used in the present invention can be obtained by converting the precursor polyarylene obtained as described above into a polyarylene having a sulfonic acid group. As this method, there are the following three methods.

(Method a) A method of deesterifying the precursor polyarylene having a sulfonate group obtained by Method A by the method described in JP-A-2004-137444.
(Method b) A method of sulfonating the precursor polyarylene obtained in Method B by the method described in JP-A-2001-342241.

(Method c) A method of introducing an alkylsulfonic acid group into the precursor polyarylene obtained by the method C by the method described in JP-A-2005-60625.
The sulfonic acid equivalent of the sulfonated polyarylene represented by the above formula (C) produced by the above method is usually 0.3 meq / g or more, preferably 0.5 to 5 meq / g, more preferably Is 0.8-3 meq / g. When the sulfonic acid equivalent is lower than the above range, the proton conductivity tends to be low and the power generation performance tends to be lowered. On the other hand, when the sulfonic acid equivalent exceeds the above range, the water resistance may be significantly lowered, which is not preferable.

  The sulfonic acid equivalent can be adjusted, for example, by changing the type, use ratio, and combination of the precursor monomer that can be the structural unit (A) and the monomer or oligomer that can be the structural unit (B).

  The molecular weight of the polyarylene having a sulfonic acid group thus obtained is 10,000 to 1,000,000, preferably 20,000 to 800,000 in terms of polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC).

[Organic solvent]
Examples of the organic solvent used in the present invention include N-methyl-2-pyrrolidone, methanol, ethanol, propanol, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, and γ-butyrolactone. , Propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether , Jiechire Glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, toluene, xylene, methyl amyl ketone, 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, 2- Methyl hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate, methyl 3-methoxypropionate, 3-methoxypropionic acid Examples thereof include ethyl, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, methyl lactate, ethyl lactate, chloroform, and methylene chloride. Among these, N-methyl-2-pyrrolidone, methanol, propanol, propylene glycol monomethyl ether, γ-butyrolactone, N, N-dimethylformamide, ethyl carbitol, and methyl carbitol are preferable. The said organic solvent may be used individually by 1 type, and may mix and use 2 or more types.

[Polyarylene composition]
The polyarylene-based composition used in the present invention contains the sulfonated polyarylene and the organic solvent, and the solid content concentration in the composition, that is, the content of the sulfonated polyarylene is based on the whole composition. Usually, it is 3 to 40% by weight, preferably 5 to 35% by weight. If the solid content concentration is lower than the above range, a coating film having a sufficient thickness may not be obtained. On the other hand, if the solid content concentration exceeds the above range, the film cannot be sufficiently cast and a uniform coating film cannot be obtained. There is.

  Moreover, the viscosity at room temperature of the composition used in the present invention is usually 1 to 1,000,000 mPa · s, preferably 10 to 100,000 mPa · s, more preferably 100 to 80,000 mPa · s, particularly Preferably it is 1000-60,000 mPa * s. If the viscosity is lower than the above range, it cannot be formed into a film at the time of coating, while if it exceeds the above range, it may not be sufficiently cast and a uniform coating film may not be obtained.

  In addition, although the composition used for this invention has the said sulfonated polyarylene and an organic solvent as a main component, you may add additives, for example, a leveling agent, a silane coupling agent, etc. as needed.

  The leveling agent is not particularly limited as long as it is a commonly used leveling agent, and for example, a fluorine-based nonionic surfactant, a special acrylic resin leveling agent, a silicone leveling agent, and the like can be used.

[Film production method]
The film manufacturing method of this invention includes the process (1) which forms a coating film by apply | coating the said polyarylene-type composition to a base | substrate, and drying.

  The method for applying the polyarylene-based composition to the substrate is not particularly limited, and for example, it can be applied using means such as a die, coater, spray, brush, roll spin coat, dipping, or screen. In addition, you may control the thickness of a film, surface smoothness, etc. by repetition of application | coating.

  The substrate used in the present invention is not particularly limited as long as it is not easily deformed by heating during drying. For example, polyethylene terephthalate (PET) film, polyethylene naphthalate (PEN) film, polybutylene terephthalate (PBT). Examples include films, nylon 6 films, nylon 6,6 films, polypropylene films, polytetrafluoroethylene films, and the like. Among these, a PET film and a PEN film are preferable because of low thermal shrinkage at high temperatures, and a PET film is more preferable because of few scratches.

  In the present invention, in order to prevent interaction with the surface treatment agent on the substrate, the substrate is preferably not surface-treated. However, the addition of particles such as silica particles or alumina particles in the film in order to obtain the slipperiness of the film is not included in the surface treatment referred to in the present invention.

  As the surface roughness of the substrate suitably used in the present invention, the center line average roughness of the surface is 0.02 μm or less, preferably 0.005 to 0.015 μm. If the center line average roughness of the surface exceeds the above range, the transfer of the electrode is not performed uniformly, and the life as a solid polymer electrolyte for a fuel cell is remarkably reduced.

  The heat shrinkage rate of the substrate suitably used in the present invention is 0.9% or less in the unwinding direction of the substrate and 0 in the width direction of the substrate under the test conditions of 150 ° C. × 30 minutes performed according to JIS C 2318. .2% or less, preferably 0.7% or less in the unwinding direction of the substrate and 0.2% or less in the width direction of the substrate. If the thermal contraction rate of the substrate exceeds the above range in the unwinding direction and the width direction of the substrate, wrinkles and the like occur in the cast film due to the thermal contraction of the substrate that occurs during drying. Such an appearance abnormality becomes a serious problem such as a starting point of fuel leakage when used for electrical / electronic materials such as proton conducting membranes.

  The substrate has a thickness of usually 25 to 250 μm, preferably 50 to 200 μm. If the thickness of the substrate is less than the above range, the rigidity of the substrate may be insufficient, and a uniform proton conductive membrane may not be obtained. On the other hand, if the thickness exceeds the above range, heat conduction during drying is poor and sufficient drying is not possible. There are things that cannot be done.

  The composition coated on the substrate can be dried by a generally used method, for example, a method of passing through a drying furnace through a number of rollers. However, in this drying process, if bubbles are generated as the solvent evaporates, the properties of the film may be significantly deteriorated. In order to prevent such deterioration of film characteristics, it is preferable to set the drying process to a plurality of steps of two or more stages and to control the temperature or the air volume in each step. Each step may be performed, for example, at 30 to 200 ° C., preferably 50 to 180 ° C., for 10 to 180 minutes, preferably 15 to 60 minutes.

The solid concentration in the film after the drying step is preferably 50 to 90% by weight, more preferably 60 to 90% by weight.
The film manufacturing method of this invention includes the process (2) which reduces content of the organic solvent which remains in the coating film formed at the said process (1).

  The peel strength (peel adhesion strength) between the substrate and the film is determined by the nature of the sulfonated polyarylene, the presence or absence of surface treatment of the substrate, the amount of residual solvent in the coating film, and the like. Therefore, in order to peel the film in a stable shape, it is necessary to further increase the solid content concentration of the film, that is, to reduce the amount of residual solvent in the film (coating film). The amount of residual solvent in 100 parts by weight of the coating film is preferably 0.5 parts by weight or less. If it exceeds 0.5 parts by weight, the adhesion between the film and the substrate becomes strong, and there is a possibility that a peeling wound or a streak may occur when peeling.

  Examples of the method for reducing the residual solvent amount include a method in which a coating film is wet-treated and dried. The coating film obtained in the above step (1) is wet-treated by, for example, immersing it in a medium such as water, alcohols, ethers, acetone or the like while being laminated on the substrate and then drying it. The amount of residual solvent in 100 parts by weight of the subsequent coating film can be reduced to 0.5 parts by weight or less. The said medium may be used individually by 1 type, may be used in mixture of 2 or more types, and may be immersed in 2 or more types of media.

When the coating film formed on the substrate is immersed in the liquid medium, the contact ratio of the medium is 10 parts by weight or more, preferably 30 parts by weight or more with respect to 1 part by weight of the coating film before the wet treatment. It is good to do. In order to minimize the residual solvent amount of the obtained film (coating film), it is preferable to maintain a contact ratio as large as possible. Also, you can change the medium used for immersion,
Maintaining the organic solvent concentration in the medium at a certain concentration or less by overflowing is also effective in reducing the amount of residual solvent in the resulting film. Further, in order to suppress the in-plane distribution of the amount of the organic solvent remaining in the film, it is preferable to homogenize the organic solvent concentration in the medium by stirring or the like.

  The temperature of the medium when dipping the film is usually in the range of 5 to 80 ° C. If the medium temperature is too high, the surface state of the film obtained after drying may be roughened. Considering the reduction efficiency of the residual solvent amount and the handleability, the range of 10 to 60 ° C. is preferable. In addition, the immersion time and the frequency | count of immersion in the liquid medium of a film can be suitably selected so that the residual solvent amount in 100 weight part of coating films may be 0.5 weight part or less.

Drying after the wet treatment can be performed by a generally used method.
The peel strength between the coating film in which the amount of residual solvent in 100 parts by weight of the coating film is reduced to 0.5 parts by weight or less by the wet treatment and the substrate is defined in JIS-K6854-2. According to the 180 degree peel test, when measured under the condition of a tensile speed of 0.7 m / min, it is desirable that the thickness is in the range of 0.05 to 2 N / width 25 mm, preferably 0.1 to 1 N / width 25 mm. . If the peel strength is lower than the above range, the adhesive force is too weak and may be peeled during drying. On the other hand, if the peel strength exceeds the above range, the adhesive force is too strong, resulting in defects such as peeling scratches and streaks. May occur.

  The thickness of the film obtained by the production method of the present invention is usually 0.1 to 1,000 μm, preferably 1 to 800 μm, more preferably 5 to 500 μm, and particularly preferably 10 to 300 μm. When the thickness of the film is below the above range, handling becomes substantially difficult. On the other hand, when the thickness exceeds the above range, proton conductivity may be reduced.

  The thickness distribution of the film obtained by the production method of the present invention is usually within ± 30%, preferably within ± 20%, more preferably within ± 15%, and particularly preferably within ± 10% with respect to the average thickness. It is. By carrying out such thickness control, local deterioration of the film can be prevented.

  The film (proton conductive membrane) obtained by the method of the present invention has a high Pronton conductivity over a wide temperature range without impairing the fuel barrier property as a film even when used for a long time. Therefore, the film obtained by the present invention is used for, for example, an electrolyte for a primary battery, an electrolyte for a secondary battery, a polymer solid electrolyte for a fuel cell, a display element, various sensors, a signal transmission medium, a solid capacitor, an ion exchange membrane, and the like. It can be suitably used as a proton conductive membrane.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. Various physical properties were determined as follows.

1. Molecular weight The molecular weight of polyarylene having no sulfonic acid group was determined by GPC using polystyrene (THF) as a solvent and the molecular weight in terms of polystyrene. The molecular weight of the polyarylene having a sulfonic acid group was determined by GPC using polystyrene as a molecular weight using N-methyl-2-pyrrolidone (NMP) to which lithium bromide and phosphoric acid were added.

2. Sulfonic acid equivalent The polymer having a sulfonic acid group was thoroughly washed until the water was neutralized, the remaining acid was removed free of charge and dried, and a predetermined amount was weighed. Titration was performed using a standard solution of NaOH using phenolphthalein dissolved in a mixed solvent of No. 1 as an indicator, and the sulfonic acid equivalent was determined from the neutralization point.

3. Appearance inspection The obtained film was peeled from the substrate in a clean room of CLASS10000, visually inspected to detect defective portions, and classified by observing with a microscope. The classification items are lines, scratches, foreign objects, and no abnormalities.

4). Surface roughness The surface roughness of the substrate is measured using a non-contact two-dimensional three-dimensional shape measuring machine “ET-30K” manufactured by Kosaka Laboratory Co., Ltd. and a surface roughness analyzer “Surfcoder AY-31”. And measured.

5. Thermal contraction rate The shrinkage rate under conditions of 150 ° C. × 30 minutes was determined according to JIS C 2318.
<Synthesis Example 1>
(1) Synthesis of polyarylene 90.3 g (225 mmol) of neopentyl 3- (2,5-dichlorobenzoyl) benzenesulfonate was added to a 1000-mL three-necked flask equipped with a stirring blade, a thermometer, and a nitrogen introduction tube. -Dichlorobenzophenone 69.1 g (275 mmol), 4-chlorobenzophenone 1.08 g (5 mmol), bis (triphenylphosphine) nickel dichloride 9.81 g (15 mmol), sodium iodide 2.25 g (15 mmol), triphenylphosphine 52 0.5 g (200 mmol) and 78.4 g (1200 mmol) of zinc were added. After the inside of the flask was vacuum-dried for 2 hours, 373 mL of dimethylacetamide (DMAc) that had been purged with dry nitrogen and dehydrated was added to initiate polymerization. Polymerization was continued for 3 hours while controlling the reaction temperature not to exceed 90 ° C., and then 1400 mL of DMAc was added to dilute the polymerization solution, and the insoluble part was filtered. The filtrate was poured into 10 L of methanol to solidify the polymer. The precipitated polymer was collected and vacuum dried to obtain 120 g of the desired polyarylene. The number average molecular weight (Mn) of the product determined by GPC was 39,000, and the weight average molecular weight (Mw) was 153,000.

(2) Synthesis of sulfonated polyarylene 120 g of polyarylene obtained in (1), 970 mL of DMAc and 29.3 g of lithium bromide (338 mmol) were added to a 300 mL three-necked flask equipped with a stirring blade, a thermometer and a nitrogen introduction tube. And stirred at 120 ° C. for 7 hours. The obtained reaction solution was poured into 5 L of acetone to solidify the polymer. The obtained solid was treated twice with distilled water / concentrated hydrochloric acid mixed solution (3.0 L / 0.37 L) and then washed with distilled water until the pH became neutral. By drying at 70 ° C. for 12 hours, 100 g of the target sulfonated polyarylene was obtained. The sulfonic acid equivalent of this polymer was 2.0 meq / g. Moreover, the weight average molecular weight (Mw) was 116,000.

<Synthesis Example 2>
(1) Synthesis of hydrophobic unit 2,2-bis (4-hydroxyphenyl) -1,1,1 was added to a 1 L three-necked flask equipped with a stirrer, thermometer, Dean-stark tube, nitrogen introduction tube and cooling tube. , 3,3,3-hexafluoropropane 20.2 g (60.2 mmol), 9,9-bis (4-hydroxyphenyl) fluorene 18.1 g (51.6 mmol), 4,4′-dichlorodiphenylsulfone 29. 6 g (103 mmol) and 20.1 g (145 mmol) of potassium carbonate were weighed. After the atmosphere in the flask was replaced with nitrogen, 170 mL of sulfolane and 85 mL of toluene were added and stirred, and the reaction solution was heated to reflux at 150 ° C. using an oil bath. Water produced by the reaction was trapped in a Dean-stark tube. After 3 hours, when almost no water was observed, toluene was removed from the Dean-stark tube out of the system. The reaction temperature was gradually raised to 200 ° C. and stirring was continued for 5 hours. Then, 10.8 g (43 mmol) of 4,4′-dichlorobenzophenone was added, and the reaction was further continued for 8 hours.

  The resulting reaction solution was allowed to cool and then diluted by adding 100 mL of toluene. Inorganic salts insoluble in the reaction solution were filtered, and the filtrate was poured into 2 L of methanol to precipitate the product. The precipitated product was filtered and dried, then dissolved in 250 mL of tetrahydrofuran, and poured into 2 L of methanol for reprecipitation. The precipitated white powder was filtered and dried to obtain 56.5 g of the target hydrophobic unit. The number average molecular weight (Mn) measured by GPC was 7,800. It was confirmed that the obtained compound was an oligomer represented by the following formula (i). In the following formula (i), the ratio of a to b (a: b) was 54:46.

(2) Synthesis of sulfonated polyarylene In a 1 L flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, 119 g (296 mmol) of neopentyl 3- (2,5-dichlorobenzoyl) benzenesulfonate was obtained in (1). 30.4 g (3.9 mmol) of a hydrophobic unit having a molecular weight (Mn) of 7,800, 5.89 g (9.0 mmol) of bis (triphenylphosphine) nickel dichloride, 1.35 g (9.0 mmol) of sodium iodide, 31.5 g (120 mmol) of triphenylphosphine and 47.1 g (720 mmol) of zinc were weighed and replaced with dry nitrogen. 350 mL of N, N-dimethylacetamide (DMAc) was added thereto, and stirring was continued for 3 hours while maintaining the reaction temperature at 80 ° C. Then, 700 mL of DMAc was added for dilution, and insoluble matters were filtered off.

  The obtained reaction solution was put into a 2 L flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, heated and stirred at 115 ° C., and 56.6 g (651 mmol) of lithium bromide was added. After stirring for 7 hours, the product was precipitated by pouring into 5 L of acetone. Next, after washing with 1N hydrochloric acid and pure water in that order, the product was dried to obtain 103 g of the desired polymer. The weight average molecular weight (Mw) of the obtained polymer was 260,000. The obtained polymer is presumed to be a sulfonated polyarylene represented by the following formula (ii). The sulfonic acid equivalent of this polymer was 2.3 meq / g.

<Synthesis Example 3>
(1) Synthesis of hydrophobic unit To a 1 L three-necked flask equipped with a stirrer, thermometer, Dean-stark tube, nitrogen inlet tube and condenser tube, 44.5 g (259 mmol) of 2,6-dichlorobenzonitrile, 9,9 -Weighed 102.0 g (291 mmol) of bis (4-hydroxyphenyl) fluorene and 52.3 g (379 mmol) of potassium carbonate. After nitrogen substitution, 366 mL of sulfolane and 183 mL of toluene were added and stirred, and the reaction solution was heated to reflux at 150 ° C. using an oil bath. Water produced by the reaction was trapped in a Dean-stark tube. After 3 hours, when almost no water was observed, toluene was removed from the Dean-stark tube out of the system. The reaction temperature was gradually raised to 200 ° C., and stirring was continued for 3 hours. Then, 16.7 g (97 mmol) of 2,6-dichlorobenzonitrile was added, and the reaction was further continued for 5 hours.

  The resulting reaction solution was allowed to cool and then diluted by adding 100 mL of toluene. Inorganic salts insoluble in the reaction solution were filtered, and the filtrate was poured into 2 L of methanol to precipitate the product. The precipitated product was filtered and dried, then dissolved in 250 mL of tetrahydrofuran, and poured into 2 L of methanol for reprecipitation. The precipitated white powder was filtered and dried to obtain 118 g of the desired hydrophobic unit. The number average molecular weight (Mn) measured by GPC was 7,300. It was confirmed that the obtained compound was an oligomer represented by the following formula (iii).

(2) Synthesis of sulfonated polyarylene To a 1 L three-necked flask equipped with a stirrer, thermometer and nitrogen introduction tube, 207.5 g (517 mmol) of neopentyl 3- (2,5-dichlorobenzoyl) benzenesulfonate, (1) 57.5 g (7.88 mmol) of hydrophobic units of Mn 7,300 obtained in
Weigh 10.3 g (15.8 mmol) of bis (triphenylphosphine) nickel dichloride, 2.36 g (15.8 mmol) of sodium iodide, 55.1 g (210 mmol) of triphenylphosphine and 82.4 g (1260 mmol) of zinc, Replaced with dry nitrogen. 720 mL of N, N-dimethylacetamide (DMAc) was added thereto, and stirring was continued for 3 hours while maintaining the reaction temperature at 80 ° C. Then, 1360 mL of DMAc was added for dilution, and insoluble matters were filtered off.

  The obtained reaction solution was put into a 2 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, heated and stirred at 115 ° C., and 98.8 g (1140 mmol) of lithium bromide was added. After stirring for 7 hours, the product was precipitated by pouring into 5 L of acetone. Subsequently, it was washed with 1N hydrochloric acid and pure water in this order and dried to obtain 223 g of the desired polymer. The weight average molecular weight (Mw) of the obtained polymer was 142,000. The obtained polymer is presumed to be a sulfonated polymer represented by the following formula (iv). The sulfonic acid equivalent of this polymer was 2.4 meq / g.

[Example 1]
130 g of the sulfonated polyarylene obtained in Synthesis Example 1 was dissolved in a mixed solvent of 348 g of methanol and 522 g of NMP to prepare a composition having a concentration of 13% by weight (solution viscosity at room temperature is 5,600 mPa · s). This composition was applied to an untreated PET film (“Tetron HSL-125” manufactured by Teijin DuPont, thickness 123 μm, width 430 mm) using an INVEX lab coater manufactured by Inoue Metal Industry. The center line average roughness of the surface of the substrate (PET film) was 0.013 μm, and the thermal shrinkage rate was 0.5% in the unwinding direction of the substrate and 0.1% in the width direction.

The PET film coated with the above composition was preliminarily dried at 80 ° C. and further dried at 140 ° C. to form a coating film (film). It was 30 weight part when the amount of residual solvents in 100 weight part of coating films was measured using 400 MHz < ¹ > H-NMR. The ratio of NMP as a residual solvent was calculated from absorption of protons of NMP appearing in the vicinity of about 2.18 ppm.

  Next, the PET film on which the coating film was formed was wet-treated by immersing it in pure water at 24 ° C. for 16 minutes. When the amount of residual solvent in 100 parts by weight of the coating film after the wet treatment was measured in the same manner as described above, it was 0.35 parts by weight. Further, after the wet treatment, the peel strength between the coating film formed on the substrate and the substrate is applied to the 180 ° peel test specified in JIS-K6854-2, and the tensile speed is 0.7 m / min. When measured below, it was 0.49 N / width 25 mm. Moreover, the film after wet processing was cut | disconnected by 300 mm space | interval, 50 sheet-like films were obtained, and the external appearance test | inspection was performed. The results are shown in Table 1.

  The electrode was heated and transferred at 150 ° C. to the substrate contact surface of the film peeled from the substrate (PET film) to obtain an electrode bonding film. When the obtained electrode bonding film was immersed in water for 1 hour to confirm the bonding property of the electrode, no peeling was confirmed.

[Example 2]
130 g of the sulfonated polyarylene obtained in Synthesis Example 2 was dissolved in a mixed solvent of 348 g of methanol and 522 g of NMP to prepare a composition having a concentration of 13% by weight (solution viscosity at room temperature is 7,000 mPa · s). This composition was applied to a PET film (“Tetron HSL-125” manufactured by Teijin DuPont Co., Ltd., thickness 125 μm) that had not been surface-treated using an INVEX lab coater manufactured by Inoue Metal Industry. The center line average roughness of the surface of the substrate (PET film) was 0.013 μm, and the thermal shrinkage rate was 0.5% in the unwinding direction of the substrate and 0.1% in the width direction.

  The PET film coated with the above composition was preliminarily dried at 80 ° C. and further dried at 140 ° C. to form a coating film. When the amount of residual solvent in 100 parts by weight of the coating film was measured in the same manner as in Example 1, it was 31 parts by weight.

Next, the PET film on which the coating film was formed was wet-treated by immersing it in pure water at 24 ° C. for 16 minutes. When the amount of residual solvent in 100 parts by weight of the coating film after the wet treatment was measured in the same manner as in Example 1, it was 0.32 parts by weight. Further, after the wet treatment, the peel strength between the coating film formed on the substrate and the substrate was measured in the same manner as in Example 1 and found to be 0.38 N / width 25 mm. In addition, an appearance inspection was performed in the same manner as in Example 1 using the film after the wet treatment. The results are shown in Table 1.

  The electrode was heated and transferred at 150 ° C. to the substrate contact surface of the film peeled from the substrate (PET film) to obtain an electrode bonding film. When the obtained electrode bonding film was immersed in water for 1 hour to confirm the bonding property of the electrode, no peeling was confirmed.

Example 3
130 g of the sulfonated polyarylene obtained in Synthesis Example 3 was dissolved in a mixed solvent of 348 g of methanol and 522 g of NMP to prepare a composition having a concentration of 13% by weight (solution viscosity at room temperature is 6,200 mPa · s). This composition was applied to a PET film (“Tetron HSL-125” manufactured by Teijin DuPont Co., Ltd., thickness 125 μm) that had not been surface-treated using an INVEX lab coater manufactured by Inoue Metal Industry. The center line average roughness of the surface of the substrate (PET film) was 0.013 μm, and the thermal shrinkage rate was 0.5% in the unwinding direction of the substrate and 0.1% in the width direction.

  The PET film coated with the above composition was preliminarily dried at 80 ° C. and further dried at 140 ° C. to form a coating film. When the amount of residual solvent in 100 parts by weight of the coating film was measured in the same manner as in Example 1, it was 31 parts by weight.

Next, the PET film on which the coating film was formed was wet-treated by immersing it in pure water at 24 ° C. for 16 minutes. When the amount of residual solvent in 100 parts by weight of the coating film after the wet treatment was measured in the same manner as in Example 1, it was 0.33 parts by weight. Further, after the wet treatment, the peel strength between the coating film formed on the substrate and the substrate was measured in the same manner as in Example 1 and found to be 0.32 N / width 25 mm. In addition, an appearance inspection was performed in the same manner as in Example 1 using the film after the wet treatment. The results are shown in Table 1.

The electrode was heated and transferred at 150 ° C. to the substrate contact surface of the film peeled from the substrate (PET film) to obtain an electrode bonding film. When the obtained electrode bonding film was immersed in water for 1 hour to confirm the bonding property of the electrode, no peeling was confirmed.

[Comparative Example 1]
130 g of the sulfonated polyarylene obtained in Synthesis Example 2 was dissolved in a mixed solvent of 348 g of methanol and 522 g of NMP to prepare a composition having a concentration of 13% by weight (solution viscosity at room temperature is 7,000 mPa · s). This composition was applied to a PET film (“Lumirror U-94” manufactured by Toray Industries, Inc., 125 μm thick) that had been subjected to surface treatment for multipurpose easy adhesion using an INVEX lab coater manufactured by Inoue Metal Industry.

  The PET film coated with the above composition was preliminarily dried at 80 ° C. and further dried at 140 ° C. to form a coating film. When the amount of residual solvent in 100 parts by weight of the coating film was measured in the same manner as in Example 1, it was 42 parts by weight.

Next, the PET film on which the coating film was formed was wet-treated by immersing it in pure water at 24 ° C. for 16 minutes. When the amount of residual solvent in 100 parts by weight of the coating film after the wet treatment was measured in the same manner as in Example 1, it was 0.33 parts by weight. Further, after the wet treatment, the peel strength between the coating film formed on the substrate and the substrate was measured in the same manner as in Example 1, and 3N / width 25 m was measured.
m. In addition, an appearance inspection was performed in the same manner as in Example 1 using the film after the wet treatment. The results are shown in Table 1.

[Comparative Example 2]
130 g of the sulfonated polyarylene obtained in Synthesis Example 2 was dissolved in a mixed solvent of 348 g of methanol and 522 g of NMP to prepare a composition having a concentration of 13% by weight (solution viscosity at room temperature is 7,000 mPa · s). This composition was applied to a PET film (“Tetron HSL-125” manufactured by Teijin DuPont Co., Ltd., thickness 125 μm) that had not been surface-treated using an INVEX lab coater manufactured by Inoue Metal Industry.

  The PET film coated with the above composition was preliminarily dried at 80 ° C. and further dried at 140 ° C. to form a coating film. When the amount of residual solvent in 100 parts by weight of the coating film was measured in the same manner as in Example 1, it was 31 parts by weight.

Next, the PET film on which the coating film was formed was wet-treated by immersing it in pure water at 24 ° C. for 5 minutes. When the amount of residual solvent after the wet treatment was measured in the same manner as in Example 1, it was 18 parts by weight. Further, after the wet treatment, the peel strength between the coating film formed on the substrate and the substrate was measured in the same manner as in Example 1 and found to be 3.4 N / width 25 mm. In addition, an appearance inspection was performed in the same manner as in Example 1 using the film after the wet treatment. The results are shown in Table 1.

[Comparative Example 3]
130 g of the sulfonated polyarylene obtained in Synthesis Example 2 was dissolved in a mixed solvent of 348 g of methanol and 522 g of NMP to prepare a composition having a concentration of 13% by weight (solution viscosity at room temperature is 7,000 mPa · s). This composition was applied to an untreated surface-treated PET film (“Tetron S-125” manufactured by Teijin DuPont Co., Ltd., thickness 125 μm) using an INVEX lab coater manufactured by Inoue Metal Industry. The center line average roughness of the surface of this substrate was 0.025 μm, and the thermal shrinkage rate was 1.0% in the unwinding direction of the substrate and 0.25% in the width direction.

The PET film coated with the above composition was preliminarily dried at 80 ° C. and further dried at 140 ° C. to form a coating film. When the amount of residual solvent in 100 parts by weight of the coating film was measured in the same manner as in Example 1, it was 31 parts by weight.

Next, the PET film on which the coating film was formed was wet-treated by immersing it in pure water at 24 ° C. for 16 minutes. When the amount of residual solvent in 100 parts by weight of the coating film after the wet treatment was measured in the same manner as in Example 1, it was 0.33 parts by weight. Further, after the wet treatment, the peel strength between the coating film formed on the substrate and the substrate was measured in the same manner as in Example 1 and found to be 0.37 N / width 25 mm. In addition, an appearance inspection was performed in the same manner as in Example 1 using the film after the wet treatment. The results are shown in Table 1.

  The electrode was heated and transferred at 150 ° C. to the substrate contact surface of the film peeled from the substrate (PET film) to obtain an electrode bonding film. When the obtained electrode bonding film was immersed in water for 1 hour to confirm the bonding property of the electrode, a part where the electrode was peeled off and the film was exposed was confirmed.

Claims (6)

A step (1) of forming a coating film by applying a polyarylene-based composition containing a polyarylene containing a sulfonic acid group and an organic solvent to a substrate and drying, and an organic solvent remaining in the coating film And (2) reducing the content of
The polyarylene has a sulfonic acid equivalent of 0.3 meq / g or more,
The content of the organic solvent remaining in 100 parts by weight of the coating film obtained in the step (2) is 0.5 parts by weight or less,
The peel strength between the coating film obtained in the step (2) and the substrate is within a range of 0.05 to 2 N / width 25 mm under the condition of a tensile rate of 0.7 m / min in a 180 degree peel test. A method for producing a film, comprising: The film production method according to claim 1, wherein the polyarylene includes a structural unit represented by the following general formula (A) and a structural unit represented by the following general formula (B).

[In the formula (A), Y represents —CO—, —SO ₂ —, —SO—, —CONH—, —COO—, —
(CF _{2) i} - _(i is an integer from 1 to 10.) Or -C (CF _{3) 2} - indicates,
Z is independently a direct bond, — (CH ₂ ) _j — (j represents an integer of 1 to 10), —C (CH ₃
) _2- , -O- or -S-
Ar is —SO ₃ H, —O (CH ₂ ) _p SO ₃ H or —O (CF ₂ ) _p SO ₃ H (p is 1 to 1).
An integer of 2 is shown. An aromatic group having a substituent represented by:
m shows the integer of 0-10, n shows the integer of 0-10, k shows the integer of 1-4. ]

[In the formula (B), A and D are each independently a direct bond, —CO—, —SO ₂ —, —SO
-, - CONH -, - COO -, - (CF 2) i -, (i is an integer of _{1~10.) - (CH 2)} j -, (j is an integer of 1 to 10.) —CR ′ ₂ — (R ′ is an aliphatic hydrocarbon group,
An aromatic hydrocarbon group or a halogenated hydrocarbon group is shown. ), Cyclohexylidene group, fluorenylidene group, -O- or -S-
B independently represents an oxygen atom or a sulfur atom;
R ^{1 to} R ¹⁶ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, a halogenated alkyl group partially or wholly halogenated, an allyl group, an aryl group, a nitro group, or a nitrile group;
s and t each represent an integer of 0 to 4, and r represents 0 or an integer of 1 or more. ] The film production method according to claim 1, wherein the substrate is polyethylene terephthalate.   The film manufacturing method according to claim 1, wherein the center line average roughness of the surface of the substrate is 0.02 μm or less.   2. The film manufacturing method according to claim 1, wherein the thermal shrinkage rate of the substrate is 0.9% or less in the unwinding direction of the substrate and 0.2% or less in the width direction of the substrate. .   The film manufacturing method according to claim 1, wherein the step (2) is performed by wet-treating and drying the coating film obtained in the step (1).