JPH0725879A - New fluorine-containing carboxilic acid anhydride and its derivative - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as a raw material for a new fluorine-containing aromatic polyimide having high stability and excellent physical properties such as low water-content, low dielectric constant and low refractive index. CONSTITUTION:A compound of the formula I (Z is fluoroalkoxy of the formula Rf'0, H or F; Rf and Rf' are l-12C fluorocarbon residue having an F/C atomic ratio of >=1), e.g. bis(1,1,2,2-tetrafluoroethoxy)pyromellitic dianhydride. The compound can be produced e.g. by reacting a fluorine-containing carboxylic acid tetraalkyl ester derivative of the formula II (R<1> to R<4> are 1-10C alkyl, H, etc.) with water in the presence of an acid catalyst and subjecting the produced new fluorine-containing carboxylic acid of the formula III to dehydrative cyclization reaction by acetic anhydride method, etc. The compound of the formula II is obtained e.g. by reacting various hydroxycarboxylic acids with a fluorine-containing olefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluorinated carboxylic acid anhydride and its derivative, and a process for producing a fluorinated polyamic acid and a fluorinated polyimide produced from them.

[0002]

2. Description of the Related Art Among various polymers, polyimide is
It has excellent heat resistance and is widely used in the aviation field, electronic and communication fields. Further, it is used as a material for an interlayer insulating film and a protective film in the field of electronic materials. In recent years, performance required for peripheral parts has been increasing along with performance miniaturization of electronic parts.

Since polyimide is generally insoluble in a solvent, it cannot be formed by a coating method when forming an insulating film or a protective film. Therefore, a solvent-soluble intermediate polyamic acid synthesized from a usual raw material diamine and tetracarboxylic acid anhydride is formed on a substrate by a coating method, and then heat-treated to form a polyimide film. In many cases
In particular, the performance required for polyimide as an electronic material is that the polyimide itself is soluble in a solvent while maintaining a low dielectric constant, a low water content, and a high softening point. Further, a low refractive index is required for optical applications.

In order to produce such a polyimide,
It is considered that these properties are exhibited by introducing a substituent having a low dielectric constant, a low hygroscopicity, and a low refractive index into tetracarboxylic dianhydride which is a monomer. For example, in JP-A-2-15084, pyromellitic dianhydride in which a perfluoroalkyl group is substituted on an aromatic ring is used, and in JP-A-2-48579, 2,4-bis (trifluoromethyl) phenoxy group is aromatic. Ring-substituted pyromellitic dianhydride, and JP-A-2-62881 describes pyromellitic dianhydride in which a fluorine-containing alkyl group is substituted on an aromatic ring.

[0005]

However, it is considered that the polyimides produced from these conventional fluorine-containing carboxylic acid anhydrides are not always sufficient in terms of stability and the like. For example, in the example described in JP-A-2-15084, the perfluoroalkyl group is directly substituted on the aromatic ring of pyromellitic dianhydride, but the aromatic ring is directly substituted. It is well known that the perfluoroalkyl group has reactivity such as hydrolysis. For example, a trifluoromethyl group and a pentafluoroethyl group are hydrolyzed into a carboxyl group and a trifluoroacetyl group, respectively [M. Hudlicky
Written by "Chemistry of Organic F
luorine Compounds, "p. 269 and p. 274, John Wiley & Sons (1
976)].

Further, these conventional fluorine-containing carboxylic acid anhydrides also have a problem that the method for introducing the fluorine-containing group is complicated. The object of the present invention, which could not be achieved by conventional polyimide, is stable, has a low water content, low dielectric constant, low refractive index, excellent physical properties such as solubility in a solvent, and is a raw material that is easily available industrially. A novel fluorine-containing aromatic polyimide, a novel fluorine-containing aromatic polyamic acid, and a fluorine-containing carboxylic acid anhydride derivative having a novel structure, which can be easily synthesized from

[0007]

Means for Solving the Problems As a result of diligent studies on the method for producing a fluorine-containing polyimide having a novel structure and properties, the present inventors have found that a carboxylic acid anhydride derivative having a fluorine-containing alkoxy group having a specific structure introduced therein. Further, they have found the fluorine-containing aromatic polyimides obtained from them and have completed the present invention.

The fluorinated alkoxy group-substituted carboxylic acid anhydride of the present invention is, as described below, perfluoroolefin, polyfluoroolefin, perfluorovinyl ether,
Fluorine-containing olefins such as chloropolyfluoroolefins and halomethanes can be extremely easily synthesized as raw materials. The method of the present invention is characterized in that a fluorine-containing alkyl group is bonded to an aromatic ring of pyromellitic dianhydride through an ether bond to form a stable structure with low reactivity. Since the fluorine-containing alkoxy group of the present invention is extremely stable both thermally and chemically, the acid anhydride of the present invention is useful as a novel high-performance fluorine-containing polyimide raw material.

That is, the present invention provides the following general formula (1)

[0010]

[Chemical 5]

(In the formula, Z is a fluoroalkoxy group represented by Rf′O, a substituent or an atom selected from a hydrogen atom and a fluorine atom. Rf and Rf ′ have a fluorine / carbon atom ratio of 1 or more. Fluorine-containing residue represented by a fluorocarbon residue having 1 to 12 carbon atoms, which may have a chlorine atom, an ether group, or a double bond, and may be different or the same. It is a carboxylic acid anhydride.

The present invention also provides the following general formula (2)

[0013]

[Chemical 6]

(In the formula, Z is a fluoroalkoxy group represented by Rf′O, a substituent or an atom selected from a hydrogen atom and a fluorine atom. Rf and Rf ′ have a fluorine / carbon atom ratio of 1 or more. represents a fluorocarbon residue having 1 to 12 carbon atoms, a chlorine atom, an ether group, the double bond may have a good .R ¹ even those same be different from each other, R ^2, R ³ and R ⁴ are each 1 to 1 carbon atoms.
A substituent or an atom selected from an alkyl group having 10 branched structures, a hydrogen atom, an alkali metal atom, and a quaternary ammonium radical, which may be different from each other or the same. ) Is a fluorine-containing carboxylic acid derivative.

The present invention also provides the following general formula (3):

[0016]

[Chemical 7]

(In the formula, Z ¹ is a fluoroalkoxy group represented by RfO, a hydrogen atom, or a substituent or atom selected from a fluorine atom. Z ² is a fluoroalkoxy group represented by Rf′O, a hydrogen atom. , A substituent or atom selected from a fluorine atom, one or both of Z ¹ and Z ² is a fluoroalkoxy group, and Rf and Rf ′ have a fluorine / carbon atom ratio of 1 or more and a carbon atom number of 1 Represents a fluorocarbon residue of ~ 12, a chlorine atom,
It may have an ether group or a double bond, and may be different or the same. A is a divalent group containing at least 2 carbon atoms. ), And the weight average molecular weight is 1 × 1.
It is a fluorine-containing polyamic acid of 0 ³ to 1 × 10 ⁷ .

The present invention also provides the following general formula (4)

[0019]

[Chemical 8]

(In the formula, Z is a full value represented by Rf'O.
Selected from oroalkoxy group, hydrogen atom and fluorine atom
It is a substituent or atom. Rf and Rf ′ are fluorine
/ Fluoro having a carbon atom ratio of 1 or more and 1 to 12 carbon atoms
Represents a carbon residue, chlorine atom, ether group, double bond
May have the same or different from each other
May be A contains at least 2 carbon atoms
It is a divalent group. ) The repeating structural unit
Containing, viscosity average molecular weight 1 ׳~ 1 x 10 ⁷And
Fluorine-containing polyimide.

In the formula (1) of the present invention, Rf and R
f'represents a fluorocarbon residue having 1 to 12 carbon atoms, and the fluorine / carbon atom ratio is preferably 1.5 or more, particularly preferably 2 or more. This fluorocarbon residue is formed by reacting a phenolic OH with a fluorine-containing olefin such as perfluoroolefin, polyfluoroolefin, perfluorovinyl ether, or chloropolyfluoroolefin in the presence of a base.

Rf and R that can be used in the present invention
f'is specifically illustrated below, but is limited to these examples only.
It is not something that will be done. For example, CHF₂-, CF₃-, C
HF ₂CF₂-, CF₃CHFCF₂-, CF₃CHFCF
(CF₃)-, (CF₃)₂CHCF₂-, (CF₃)₂CH
CF (CF₂CF₃)-, CF₂= CF-, CFClHC
F₂-, CF₂= CFCF₂-, CF₃CF = CF-, (C
F₃)₂C = CF-, (CF₃)₂C = C (CF₂CF₃)
-, C₉F₁₇-, CF₃CF₂CF₂OCHFCF₂-, C
F₃CF₂CF₂OCF (CF₃) CF₂OCHFCF₂-N
Which can be mentioned.

The fluorocarbon residue may be formed by any method, but one of the preferred methods for forming a fluorocarbon residue having 2 or more carbon atoms is to use a phenolic OH and a peroxidic group in the presence of a base. Fluoro olefins,
It is a method of forming by reaction with a fluorine-containing olefin such as polyfluoroolefin, perfluorovinyl ether, and chloropolyfluoroolefin. The case of perfluoroolefin is shown in the following general formula (5).

[0024]

[Chemical 9]

The number of carbon atoms of the perfluoroolefin is not particularly limited, but those having 2 to 12 carbon atoms, preferably 2 to 9 carbon atoms are usually used because of easy availability and handling. In addition, a part, preferably one, of the fluorine atoms of the perfluoroolefin may be replaced with a chlorine atom. As an example of the similar reaction between the above-mentioned phenolic OH and perfluoroolefin, for example, the following reactions are known.

1) J. Amer. Chem. Soc. ，
vol. 82, 5116 (1960)

[0027]

[Chemical 10]

2) The Chemical Society of Japan, 1975, (2) p3
11 reactions

[0029]

[Chemical 11]

One of the preferable methods for forming the fluorocarbon residue having 1 carbon atom is the following general formula (8):

[0031]

[Chemical 12]

(Wherein X is an atom selected from Cl, Br, I and H, and Y is an atom selected from F, Cl, Br and I). As described above, it is formed by reacting with a phenol derivative in the presence of a base in a polar solvent.

[0033]

[Chemical 13]

The following reaction is known as an example of the similar reaction between the above-mentioned phenolic OH and halomethane. 1) J. Org. Chem. , Vol. 25,2009
The reaction described in (1960)

[0035]

[Chemical 14]

2) J. Amer. Chem. Soc. ，
vol. 77, 6618 (1955)

[0037]

[Chemical 15]

Another preferable method of forming a fluorocarbon residue having 1 carbon atom is to react a trichloromethoxy derivative with hydrogen fluoride as shown in the following formula (12).

[0039]

[Chemical 16]

The following reactions are known as examples of similar reactions between the above trichloromethoxy derivative and hydrogen fluoride. 1) Reaction described in British Patent 765527

[0041]

[Chemical 17]

The RfO group (and Rf′O group) of the present invention is characterized in that it is a fluorine-containing substituent which is chemically stable and has high flexibility. The fluorine-containing alkoxy group (RfO of the present invention
-, Rf'O- and the like) is a perfluoroalkoxy group, a polyfluoroalkoxy group, or a perfluoroalkenyloxy group, and may have a chlorine atom or an ether bond. [1] At least one, preferably two or more fluorine atoms are bonded to the carbon atom of Rf and Rf ′ bonded to the oxygen atom of the RfO group and Rf′O group, or [2] ] A structure in which an unsaturated bond is bonded is preferable. In particular, the carbon atom bonded to the oxygen atom of the RfO group and the Rf′O group is not bonded to a hydrogen atom, and the following formula (14)

[0043]

[Chemical 18]

(In the formula, R ⁹ , R ¹⁰ and R ¹¹ represent a fluorocarbon residue having a total of 3 to 10 carbon atoms, a hydrogen atom or a fluorine atom, a chlorine atom, an ether group, It may have a double bond) or the following formula (15).

[0045]

[Chemical 19]

(In the formula, R ¹² , R ¹³ , R ¹⁴ and R ^{15 each} represent a fluorocarbon residue having a total of 4 to 9 carbon atoms, a hydrogen atom or a fluorine atom, a chlorine atom or an ether). Group, may have a double bond) or the following formula (16)

[0047]

[Chemical 20]

(In the formula, R ¹⁶ and R ¹⁷ represent a fluorocarbon residue having a total of 2 to 10 carbon atoms, a hydrogen atom or a fluorine atom, and a chlorine atom, an ether group or a double bond. May be included) or the following formula (1
7)

[0049]

[Chemical 21]

(In the formula, R ¹⁸ and R ¹⁹ represent a fluorocarbon residue, a hydrogen atom or a fluorine atom, and may have a chlorine atom, an ether group or a double bond.
f ″ represents a fluorocarbon residue. R ¹⁸ , R ¹⁹ , R
The total number of carbon atoms of f ″ is 1 to 10. The case of RfO (and Rf′O) having the structure exemplified in () is particularly preferable because it is thermally and chemically stable. The fluorine-containing carboxylic acid anhydride of the present invention can be produced by various methods. For example, the following formula (18)

[0051]

[Chemical formula 22]

A method for producing by a cyclodehydration reaction of a fluorine-containing carboxylic acid represented by the following formula (19)

[0053]

[Chemical formula 23]

Examples thereof include a method for producing the fluorine-containing carboxylic acid dialkyl ester by an intramolecular transesterification reaction, and a method for producing the fluorine-containing carboxylic acid by dehydration is particularly preferable. In the above formula (19), R
¹ and R ² are alkyl groups having 1 to 10 carbon atoms and may have a branched structure, and R ¹ and R ² may be different from each other or may be the same. Examples of R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, 1-
Methylpropyl, 2-methylpropyl, pentyl and the like are used.

The dehydration cyclization reaction of the fluorine-containing carboxylic acid can be carried out by a usual method. For example, an acid anhydride method such as an acetic anhydride method or a heat dehydration method can be used. The fluorinated carboxylic acid of the present invention can be produced by various methods. For example, the following formula (20)

[0056]

[Chemical formula 24]

(In the formula, R ¹ , R ² , R ³ and R ⁴ may have a branched structure having 1 to 10 carbon atoms, an alkyl group, a hydrogen atom, an alkali metal atom and a quaternary ammonium radical. A fluorine-containing carboxylic acid tetraalkyl ester derivative represented by a substituent or atom selected from the following, which may be different or the same as each other.) In the presence of an acid catalyst or a base catalyst. And the method of hydrolysis is mentioned.

Another reaction for producing the fluorine-containing carboxylic acid of the present invention is represented by the following formula (21)

[0059]

[Chemical 25]

(In the formula, R ⁵ , R ⁶ , R ⁷ , and R ⁸ are usually an alkyl group having 1 to 10 carbon atoms, preferably 1 carbon atom, and optionally having a branched structure, or chlorine. A substituted alkyl group or a hydroxyl group-substituted alkyl group, which may be different from each other or the same).
A method of producing the fluorine-containing tetraalkylbenzene derivative by oxidation is mentioned.

The oxidation method in this reaction may be any reaction as long as it is a reaction for converting a side chain alkyl group of a benzene ring into a carboxyl group, and various methods can be used.
As the oxidizing agent, for example, permanganate, chromic acid, dichromate, lead dioxide, halogen, nitric acid, nitro compound, nitrogen dioxide-selenium dioxide, oxygen and the like are used.

The conditions of this reaction will differ depending on the starting materials used, but are usually carried out under the conditions described below, depending on the type of oxidizing agent used. When using a nitro compound as an oxidant: Fluorine-containing tetraalkylbenzene is heated in the presence of an alkali to react with the nitro compound. The reaction temperature is usually 0 to 300 ° C., preferably 5
It is carried out at 0 to 250 ° C. As the nitro compound, usually an aromatic nitro compound or an aliphatic nitro compound, preferably an aromatic nitro compound is used. As the alkali, an alkali metal hydroxide, an alkali metal oxide, an alkaline earth hydroxide or an alkaline earth oxide is usually used. A solvent inert to the reaction may be used.

When nitric acid is used as an oxidizing agent: Fluorine-containing tetraalkylbenzene is reacted with heating nitric acid. The reaction temperature is generally 0 to 300 ° C, preferably 50 to 200 ° C. The nitric acid concentration is usually 5 to 1
00%, preferably 20 to 100% is used. When nitrogen dioxide-selenium dioxide is used as an oxidizing agent: Fluorine-containing tetraalkylbenzene and selenium are added to an inert organic solvent, and the reaction is carried out by heating while blowing nitrogen dioxide. The reaction temperature is generally 0 to 300 ° C, preferably 50 to 250 ° C.

When oxygen is used as an oxidizing agent [1] Auto-oxidation in the presence of base: Fluorine-containing tetraalkylbenzene is reacted with oxygen in the presence of a base in a polar solvent. Dimethyl sulfoxide, diphenyl sulfoxide, hexamethylphosphoramide, and dimethylformamide are used as the polar solvent. The reaction temperature is usually -20 to 200.
C., preferably 0-100.degree.

When oxygen is used as an oxidant [2] Autoxidation in the presence of catalyst: Fluorine-containing tetraalkylbenzene is reacted with oxygen in the presence of catalyst. Usually, a cobalt salt, a vanadium salt, a manganese salt, a copper salt or a lead salt is used as the catalyst. Alternatively, a halide may be used as a cocatalyst.
An example of a preferred catalyst system is cobalt (II) acetate-
Hydrogen bromide-acetic acid system, cobalt (II) acetate-hydrochloric acid system, cobalt (II) acetate-sodium chloride system, cobalt (II) acetate-ammonium bromide system and the like are used.

When lead dioxide is used as an oxidizing agent: Fluorine-containing tetraalkylbenzene is heated in the presence of alkali to react with lead dioxide. The reaction temperature is generally 0 to 300 ° C, preferably 100 to 250 ° C. As the alkali, an alkali metal hydroxide, an alkali metal oxide, an alkaline earth hydroxide or an alkaline earth oxide is usually used. A solvent inert to the reaction may be used.

When chromic acid or dichromate is used as an oxidant: chromic acid mixture, chromium (VI) oxide-sulfuric acid, chromium (VI) oxide-acetic acid, sodium dichromate-sulfuric acid, sodium dichromate aqueous solution, etc. The fluorine-containing tetraalkylbenzene is reacted in the oxidizing agent. The reaction temperature is generally -20 to 300 ° C, preferably 0 to 250.
It is performed at ℃.

When using permanganate as an oxidant: potassium permanganate is reacted with fluorine-containing tetraalkylbenzene in a solvent such as water, nitric acid or pyridine. The reaction temperature is generally 0 to 300 ° C., preferably 50.
It is performed at ˜200 ° C. Various methods can be used as a method for introducing a fluorine residue for synthesizing the fluorinated carboxylic acid derivative and the fluorinated tetraalkylbenzene of the present invention. For example, the formula (22), the formula (23), and the formula (24) ,
As shown in the formula (25), a method of producing various hydroxycarboxylic acid derivatives or hydroxytetraalkylbenzene by reacting with a fluorinated olefin in the presence of a base catalyst in a polar solvent is used.

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

[In the above formulas (22) and (23), R
f ¹ and Rf ¹ 'represent a fluorocarbon residue having 2 to 12 carbon atoms. R ¹ , R ² , R ³ , and R ⁴ have 1 to 10 carbon atoms.
10 are alkyl groups which may have a branched structure, hydrogen atoms, and substituents or atoms selected from alkali metals, which may be different or the same.
Z ³ is a hydrogen atom or a fluorine atom. ]

[0072]

[Chemical 28]

[0073]

[Chemical 29]

[In the above formulas (24) and (25), R
f ¹ and Rf ¹ 'represent a fluorocarbon residue having 2 to 12 carbon atoms. R ⁵ , R ⁶ , R ⁷ , and R ⁸ are usually an alkyl group, a chlorine-substituted alkyl group, or a hydroxyl-substituted alkyl group having 1 to 10 carbon atoms, preferably 1 carbon atom, which may have a branched structure. Groups, which may be different or the same. Z ³ is a hydrogen atom or a fluorine atom. The fluorine-containing olefin used in the present invention may be any one as long as it reacts with a phenolic hydroxyl group to form Rf. For example, CF
₂ = CF ₂ , CF ₃ CF = CF ₂ , CF ₃ CF = CFCF ₃ ,
(CF ₃ ) ₂ C = CF ₂ , CF ₂ = CFCl, Formula (24)
An oligomer of hexafluoropropene (HFP) represented by: or an oligomer of tetrafluoroethylene (TFE) represented by the formula (Formula 25), CF ₂ ═CFOCF
₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF (CF ₃ ) OC
Examples thereof include perfluorovinyl ether such as F ₂ CF ₂ CF ₃ .

[0075]

[Chemical 30]

[0076]

[Chemical 31]

The conditions of this reaction will differ depending on the kinds of raw materials used, but they are usually carried out under the conditions described below. As the base catalyst, various bases can be used. For example, NaOH, an alkali metal hydroxide, NaHCO _3, KHCO alkali metal bicarbonate salts such as _3, an alkali metal carbonate such as _{Na 2 CO 3, K 2 CO} 3, triethylamine, amines such as tributylamine, such as KOH , And alkali metals such as metallic Na and alkaline earth metals. The amount of the base catalyst is usually expressed as a molar ratio to the dihydroxycarboxylic acid derivative used and is usually 0.0
01 to 10.0, preferably 0.01 to 2.0 is used.

As the polar solvent used in this reaction, various polar solvents can be used. For example, dimethyl sulfoxide, dimethylformamide, sulfolane, N
-Methylpyrrolidone, acetone, tetrahydrofuran,
Examples thereof include dioxane, tetraglyme, dimethoxyethane and the like. The amount of the polar solvent is usually 10 to 1000% by weight based on the dihydroxycarboxylic acid derivative used.

The reaction temperature is usually 0 to 150 ° C., preferably 40 to 100 ° C., and the reaction pressure is usually 0.1 to 20 kg.
/ Cm ² -G, preferably 0.1-10 kg / cm ² -G
Done in. In addition, in this reaction, hydrogen-containing fluorine-containing alkyl substitution product (Rf = C _m
The selectivity of F _2m H, m: an integer of 2 to 12) can be increased.

Other reactions for obtaining the fluorinated carboxylic acid derivative or the fluorinated tetraalkylbenzene of the present invention include formula (28), formula (29), formula (30) and formula (31)
Also useful is a method of producing various hydroxycarboxylic acid derivatives or hydroxytetraalkylbenzenes represented by the formula (1) by reacting with halomethane in the presence of a base catalyst in a polar solvent.

[0081]

[Chemical 32]

[0082]

[Chemical 33]

[In the above formula (28) and formula (29), R
¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 to 10 carbon atoms which may have a branched structure, a hydrogen atom, a substituent or an atom selected from an alkali metal, and are the same or different. It may be one. Z ³ is a hydrogen atom or a fluorine atom. ]

[0084]

[Chemical 34]

[0085]

[Chemical 35]

[In the above formulas (30) and (31), R
⁵ , R ⁶ , R ⁷ , and R ⁸ are usually an alkyl group having 1 to 10 carbon atoms, preferably 1 carbon atoms, which may have a branched structure, a chlorine-substituted alkyl group, or a hydroxyl-substituted alkyl group. Yes, they may be different or the same. Z ³ is a hydrogen atom or a fluorine atom. ]
The halomethane used in this reaction is represented by the following general formula (32)

[0087]

[Chemical 36]

(Wherein X is an atom selected from Cl, Br, I and H, and Y is an atom selected from Cl, Br and I). Dibromodifluoromethane, bromodifluoromethane and chlorodifluoromethane are preferably used. The conditions for this reaction will differ depending on the types of raw materials used, but they are usually carried out under the conditions described below.

As the base catalyst, various bases can be used. For example, NaOH, an alkali metal hydroxide, NaHCO _3, KHCO alkali metal bicarbonate salts such as _3, an alkali metal carbonate such as _{Na 2 CO 3, K 2 CO} 3, triethylamine, amines such as tributylamine, such as KOH , And alkali metals such as metallic Na and alkaline earth metals. The amount of the base catalyst is usually 0.00 in terms of the molar ratio to the dihydroxycarboxylic acid derivative or dihydroxytetraalkylbenzene used.
1 to 10.0, preferably 0.01 to 2.0 is used.

As the polar solvent used in this reaction, various polar solvents can be used. For example, dimethyl sulfoxide, dimethylformamide, sulfolane, N
-Methylpyrrolidone, acetone, tetrahydrofuran,
Examples thereof include dioxane, tetraglyme, dimethoxyethane and the like. The amount of the polar solvent is usually 10 to 1000% by weight based on the dihydroxycarboxylic acid derivative used.

The reaction temperature is usually 0 to 150 ° C., preferably 40 to 100 ° C., and the reaction pressure is usually 0.1 to 20 kg.
/ Cm ² -G, preferably 0.1-10 kg / cm ² -G
Done in. As still another reaction for obtaining the fluorine-containing carboxylic acid derivative or fluorine-containing tetraalkylbenzene of the present invention, as exemplified in the case of the dihydroxycarboxylic acid derivative and dihydroxytetraalkylbenzene in the following formulas (33) and (34), It is also possible to use a method in which the phenolic hydroxyl group of various hydroxycarboxylic acid derivatives or hydroxytetraalkylbenzene is trichloromethylated and then treated with hydrogen fluoride to obtain a trifluoromethyl derivative. Further, in the case of monohydroxycarboxylic acid derivative and monohydroxytetraalkylbenzene, it can be produced by the same method.

[0092]

[Chemical 37]

(In the formula, R ¹ , R ² , R ³ , and R ⁴ may have a branched structure having 1 to 10 carbon atoms, an alkyl group, a hydrogen atom, an alkali metal atom, and a quaternary ammonium radical. Substituents or atoms selected from, and they may be different from each other or the same.)

[0094]

[Chemical 38]

(In the formula, R ⁵ , R ⁶ , R ⁷ and R ⁸ are usually an alkyl group having 1 to 10 carbon atoms, preferably 1 carbon atom, which may have a branched structure, or chlorine. Substituted alkyl groups or hydroxyl-substituted alkyl groups, which may be different or the same as each other.) The weight average molecular weight of the fluorine-containing polyamic acid represented by the formula (3) of the present invention is 1 × 10 ^3. ˜1 × 10 ⁷ , preferably 2 × 10 ³
To 3 × 10 ⁶ , more preferably 5 × 10 ³ to 1 × 10
^{Is 6} . The weight average molecular weight can be determined by measuring using gel permeation chromatography (polystyrene standard).

Fluorine-containing immisions represented by the formula (4) of the present invention
Viscosity average molecular weight is 1 × 10³~ 1 x 10⁷, Preferred
2 × 10³~ 3 x 10⁶, And more preferably 5 ×
10 ³~ 1 x 10⁶Is. The viscosity average molecular weight is
A concentrated sulfuric acid solution of the polymer is prepared and measured (Piromellit
Acid anhydride and 4,4'-diaminodiphenyl ether
Based on the molecular weight of the polyimide obtained from the above. )
You can ask more.

The fluorinated polyamic acid and the fluorinated polyimide of the present invention may be produced by any method, but one preferable example of the production method is the above-mentioned general formula (1).
And a fluorine-containing carboxylic acid anhydride represented by the following general formula (3
5)

[0098]

[Chemical Formula 39]

A diamine of the formula A is a divalent radical containing at least two carbon atoms, the two amino radicals being bound to another carbon atom of the divalent radical. Is prepared in the presence of an inert solvent to prepare a fluorinated polyamic acid solution, and then the fluorinated polyamic acid is ring-closed to give a fluorinated polyimide. In the present invention, both the diamine component and the tetracarboxylic acid anhydride component may be used as a single component, or a plurality of diamine components and tetracarboxylic acid components may be mixed and used. In either case, the total number of moles of multiple or single diamines and the total number of moles of multiple or single tetracarboxylic anhydrides are equal or nearly equal.

As the diamine used in this reaction, any diamine that is generally used as a diamine component of polyimide can be used. Further, a fluorine-containing diamine may be used as the diamine. Normal,
m-phenylenediamine, p-phenylenediamine,
4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4 ' -Diaminodiphenyl ether, bis (4
-Aminophenyl) diethylsilane, bis (4-aminophenyl) phosphine oxide, bis (4-aminophenyl) -N-methylamine, 1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 3,3′-dimethoxybenzidine, 2,4-bis (β-amino-t-butyl) toluene, bis (p-β-
Amino-t-butylphenyl) ether, p-bis (2
-Methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene,
Bis (p-aminocyclohexyl) methane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 3-methylheptamethylenediamine, 4,4′-
Dimethylheptamethylenediamine 2,11-diaminododecane, 1,2-bis (3-aminopropoxy) ethane, 2,2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 2, 5-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,12-diaminooctadecane, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2 , 4-diaminodurene, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-diaminobenzotrifluoride, bis (trifluoromethyl) phenylenediamine,
3,3'-dimethyl-4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 2,2'-bis (trifluoromethyl)
-4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl,
2,2-bis (p-aminophenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) -4,
4'-diaminodiphenyl ether, 3,3'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether and the like are used. In the present invention, 2,2
-Bis [3-amino-4- (1,1,2,2-tetrafluoroethoxy) phenyl] hexafluoropropane,
3,3'-diamino-4,4'-bis (1,1,2,2
A polyfluoroalkoxy group-substituted aromatic diamine such as -tetrafluoroethoxy) biphenyl may also be used.
These polyfluoroalkoxy group-substituted aromatic diamines are 3,3′-diamino-4,4′-bis (1,1,1
Taking 2,2-tetrafluoroethoxy) -biphenyl as an example, 3,3′-bis (acetylamino)-
3,4'-dihydroxybiphenyl obtained by adding tetrafluoroethylene in the presence of a base catalyst,
3'-bis (acetylamino) -4,4'-bis (1,
It can be synthesized by hydrolyzing 1,2,2-tetrafluoroethoxy) -biphenyl.

When the tetracarboxylic acid anhydride component is used as a plurality of mixtures, examples of the tetracarboxylic acid component which can be used in combination with the fluorine-containing carboxylic acid anhydride of the present invention include pyromellitic dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 1,4,5,6-
Naphthalenetetracarboxylic dianhydride, 3,3 ', 4
4'-biphenyltetracarboxylic dianhydride, 1,2,
5,6-naphthalenetetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride Anhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) propane dianhydride, 1 , 1-bis (2,3-dicarboxyphenyl) ethane dianhydride,
1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3 , 3 ′, 4,4′-tetracarboxydiphenyl ether dianhydride, 2,3 ′, 3,4′-tetracarboxydiphenyl ether dianhydride and the like.
Also, 2,2-bis (3,4-dicarboxyphenyl)
A fluorine-containing tetracarboxylic acid anhydride such as hexafluoropyropanane dianhydride may be used.

The solvent used in the preparation of the polyamic acid is usually N, N-dimethylformamide, N,
N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, tetramethylurea, dimethylsulfone, hexamethylphosphoamide, sulfolane and the like are used. These solvents may be used alone or may be mixed with each other. Also, Freon-113
You may add and use a solvent, such as.

The reaction temperature at the time of preparing the polyamic acid varies depending on the kind of raw material, but it is usually from -20 to 100 ° C. As a method for producing a film of fluorine-containing polyimide, for example, a fluorine-containing polyamic acid solution is cast or spin-coated on a substrate such as a quartz plate or a silicon wafer to form a film, and stepwise heating is performed under a nitrogen atmosphere. A method for obtaining a fluorinated polyimide film can be mentioned.

[0104]

EXAMPLES Examples of the present invention will be specifically described below, but the present invention is not limited to these examples. In each of the following examples, imidation was confirmed by characteristic absorption due to symmetrical stretching vibration and asymmetric stretching vibration of the carbonyl group in the infrared absorption spectrum. In addition, the polyimide film formed on a silicon wafer was vacuum dried at 120 ° C for 2 hours, and then left in a constant temperature and humidity chamber at 24 ° C and a relative humidity of 50% for 24 hours to determine the water absorption of the polyimide film from the weight change before and after. It was measured.

The weight average molecular weight of the present invention was measured by gel permeation chromatography (polystyrene standard). The viscosity average molecular weight of the polymer was measured by adjusting a concentrated sulfuric acid solution of the polymer. (Based on the molecular weight of the polyimide obtained from pyromellitic anhydride and 4,4′-diaminodiphenyl ether.)

[0106]

Example 1 [Synthesis of fluorine-containing carboxylic acid tetraalkyl ester]
Dihydroxypyromellitic acid tetraethyl ester 8.
0 g, 0.56 g of potassium hydroxide, and 200 ml of dimethyl sulfoxide were placed in a three-neck flask with an internal volume of 1 l.
The mixture was stirred at 60 ° C for 2 hours. Reaction mixture made of stainless steel 1
3. The autoclave was charged, the system was replaced with nitrogen gas, and then tetrafluoroethylene gas was introduced to adjust the pressure to 4.
It was set to 0 kg / cm ² -G. The autoclave was heated to 90 ° C. with stirring. Since the pressure decreases with the progress of the reaction, tetrafluoroethylene gas is appropriately introduced,
The reaction was carried out for 70 hours while maintaining the pressure in the system at 3.0 to 4.0 kg / cm ² -G. After completion of the reaction, dimethyl sulfoxide was distilled off from the reaction solution, 20 ml of water and 20 ml of methylene chloride were added, and the mixture was stirred. The organic phase was separated and methylene chloride was distilled off to obtain 10 g of white crystals having a melting point of 149 to 150 ° C. (yield 80%). These are shown in Table 1 as mass spectrum, infrared absorption spectrum, and ¹ H
-From the measurement results of NMR, the following formula (36)

[0107]

[Chemical 40]

The target compound bis (1,1,
It was confirmed to be 2,2-tetrafluoroethoxy) pyromellitic acid tetraethyl ester. The infrared absorption spectrum of this product is shown in FIG. [Synthesis of Fluorine-Containing Carboxylic Acid] Bis (1,1,2,2-
Tetrafluoroethoxy) pyromellitic acid tetraethyl ester 2.0 g (3.3 mmol), H ₂ O 25 m
1, potassium hydroxide 3.0g, and ethanol 30m
1 was placed in a three-necked flask having an inner volume of 100 ml and stirred at 80 ° C. for 3 hours. By adding 2.5 M sulfuric acid aqueous solution to the reaction solution to make it acidic, 1.5 g of white crystals having a melting point of 265 ° C. was obtained (3.1 mmol, yield 94%). This is shown in Table 1 from the infrared absorption spectrum and the ¹ H-NMR measurement result, and the following formula (37)

[0109]

[Chemical 41]

Bis (1,1,1, which is the target compound, shown in
It was confirmed to be 2,2-tetrafluoroethoxy) pyromellitic acid. The infrared absorption spectrum of this product is shown in FIG. [Synthesis of Fluorine-Containing Carboxylic Anhydride] Bis (1,1,
2,2-tetrafluoroethoxy) pyromellitic acid
4 g (2.9 mmol) and 21 g of acetic anhydride were included in the content 50
The mixture was placed in a ml flask and stirred at 70 ° C. for 3 hours. The reaction solution was filtered to obtain 1.0 g of crystals (2.2 mmol, yield 76%). As shown in Table 1, this product has an infrared absorption spectrum of 1770 cm ^-1 and 1859 cm ^-1.
Since the characteristic absorption of acid anhydride is shown in, the following formula (38)

[0111]

[Chemical 42]

Bis (1,1,1, which is the target compound, shown in
It was confirmed to be 2,2-tetrafluoroethoxy) pyromellitic dianhydride. The infrared absorption spectrum of this product is shown in FIG. [Synthesis of Fluorine-Containing Polyimide] 0.400 g (2.00 mmol) of 4,4′-diaminodiphenyl ether was added to N
A solution of methylpyrrolidone in 2.9 g and bis (1,1,2,2-tetrafluoroethoxy) pyromellitic dianhydride 0.900 g (2.00 mmol) in N were added.
-Mixing the solution dissolved in 4.0 g of methylpyrrolidone,
A uniform solution of polyamic acid was obtained by stirring at room temperature for 50 hours under a nitrogen atmosphere. The weight average molecular weight of this polyamic acid was 1.3 million. The infrared absorption spectrum of the polyamic acid after the solvent was distilled off is shown in FIG. A polyimide film was obtained by spin-coating a polyamic acid solution on a silicon wafer to form a film, and heating and curing under nitrogen at 140 ° C. for 30 minutes and 350 ° C. for 1 hour. The infrared absorption spectrum of this product is shown in FIG. Since characteristic absorption was observed in the infrared absorption spectrum, it was confirmed to be a polyimide. The water absorption was 0.24%.
The viscosity average molecular weight of the polyimide was 900,000.

[0113]

[Table 1]

[0114]

Example 2 Synthesis of Fluorine-Containing Tetraalkylbenzene 240 ml of acetic acid was added to a 500 ml flask equipped with a stirrer and a reflux condenser.
1, water 60 ml, tetramethyl-p-benzoquinone 10
g and 15 g of zinc powder were added, and the mixture was stirred for 6 hours while refluxing under a nitrogen gas atmosphere. After removing unreacted zinc in the reaction solution by decantation, the reaction solution was cooled. The precipitated crystals of tetramethyl-p-hydroquinone were filtered under a nitrogen stream and washed with water. 300m of this crystal
1 Micro-bomb, potassium hydroxide 1.68g,
50 ml of dimethylformamide was added, the system was replaced with nitrogen, and the mixture was stirred at 80 ° C. for 2 hours. Next, tetrafluoroethylene was fed at a pressure of 4 kg / cm ₂ -G,
The mixture was stirred at 90 ° C for 30 hours. After completion of the reaction, dimethylformamide was distilled off from the reaction solution, and diethyl ether 150 was added.
ml and 150 ml of water were added and stirred. The organic phase was separated, and the ether was distilled off to obtain 18.8 g of white crystals having a melting point of 83 to 84 ° C (yield 84%). This product has mass spectrum, infrared absorption spectrum and ¹ H-NMR.
From the measurement result of the following formula (39)

[0115]

[Chemical 43]

The desired compound 1,4-bis (1,1,2,2-tetrafluoroethoxy) -2, shown in
It was confirmed to be 3,5,6-tetramethylbenzene. [Synthesis of fluorinated carboxylic acid] 1,4-bis (1,1,
2,2-tetrafluoroethoxy) -2,3,5,6-
Tetramethylbenzene 10 g, pyridine 180 ml, and water 90 ml were placed in a 500 ml flask, the temperature was raised to 90 ° C., potassium permanganate 22.4 g was added, and the mixture was stirred under reflux for 3 hours. After manganese dioxide in the reaction solution was filtered, the solvent in the filtrate was distilled off with an evaporator. To the obtained solid, 240 ml of a 6% sodium hydroxide aqueous solution was added, and the temperature was raised to 100 ° C. to dissolve the solid, 26.7 g of potassium permanganate was added, and the mixture was stirred at 100 ° C. for 1.5 hours. Ethanol was added to decompose excess potassium permanganate and filtered. After cooling the filtrate, dilute hydrochloric acid was added to acidify the solution to deposit a precipitate. After filtering this precipitate off,
Recrystallization from water gave 6.7 g of white crystals (yield 91
%).

This has an infrared absorption spectrum and ¹ H
From the NMR measurement results, the target compound bis (1,
It was confirmed to be 1,2,2-tetrafluoroethoxy) pyromellitic acid (Chemical Formula 37).

[0118]

Example 3 [Synthesis of Fluorine-Containing Carboxylic Acid Tetraalkyl Ester]
Crystals were obtained by the same method as in the synthesis of the fluorine-containing carboxylic acid tetraalkyl ester of Example 1 except that chlorotrifluoroethylene was introduced instead of tetrafluoroethylene (yield 87%). From the results of mass spectrum measurement, infrared absorption spectrum measurement and ¹ H-NMR analysis, the following formula (40)

[0119]

[Chemical 44]

Bis (2-chloro-1,1,2-
Trifluoroethoxy) pyromellitic acid tetraethyl ester, and the following formula (41)

[0121]

[Chemical formula 45]

Bis (2-chloro-1,2-difluoroethenyloxy) pyromellitic acid tetraethyl ester represented by the following formula (42)

[0123]

[Chemical formula 46]

3- (2-chloro-1,2-difluoroethenyloxy) -6- (2-chloro-1,1, shown in
It was confirmed to be a mixture of three kinds of 2-trifluoroethoxy) pyromellitic acid tetraethyl ester.

[0125]

Example 4 [Synthesis of Fluorine-Containing Carboxylic Acid Tetraalkyl Ester]
In the same manner as in the synthesis of the fluorine-containing carboxylic acid tetraalkyl ester of Example 1, except that hexafluoropropylene was introduced instead of tetrafluoroethylene,
Crystals were obtained (yield 84%). From the results of mass spectrum measurement, infrared absorption spectrum measurement and ¹ H-NMR analysis, the following formula (43)

[0126]

[Chemical 47]

Bis (1,1,2,3,3,3-hexafluoropropoxy) pyromellitic acid tetraethyl ester represented by: and the following formula (44)

[0128]

[Chemical 48]

Bis (1,2,3,3,3-pentafluoropropenyloxy) pyromellitic acid tetraethyl ester represented by the following formula (45)

[0130]

[Chemical 49]

3- (1,2,3,3,3-pentafluoropropenyloxy) -6- (1,1,2,3, shown in
It was confirmed to be a mixture of three types of 3,3-hexafluoropropoxy) pyromellitic acid tetraethyl ester.

[0132]

Example 5 [Synthesis of Fluorine-Containing Carboxylic Acid Tetraalkyl Ester]
Crystals were obtained by the same method as in the synthesis of the fluorine-containing carboxylic acid tetraalkyl ester of Example 1 except that heptafluoropropyl trifluorovinyl ether was used instead of tetrafluoroethylene (yield 78%). From the results of mass spectrum measurement, infrared absorption spectrum measurement and ¹ H-NMR analysis, the following formula (46)

[0133]

[Chemical 50]

It was confirmed to be bis (2-heptafluoropropoxy-1,1,2-trifluoropropoxy) pyromellitic acid tetraethyl ester shown in (1).

[0135]

Example 6 [Synthesis of Fluorine-Containing Tetraalkylbenzene] The procedure of Example 1 was repeated except that 2,3,5,6-tetramethylphenol was used instead of tetramethyl-p-hydroquinone. 1- (1,1,2,2-tetrafluoroethoxy) -under the same conditions as in the synthesis
2,3,5,6-Tetramethylbenzene was obtained. [Synthesis of fluorinated carboxylic acid] 1,4-bis (1,1,
2,2-tetrafluoroethoxy) -2,3,5,6-
1- (1,1,2,2 instead of tetramethylbenzene
-Tetrafluoroethoxy) -2,3,5,6-tetramethylbenzene was used, and crystals were obtained in the same manner as in the synthesis of the fluorine-containing carboxylic acid of Example 1 (yield 9
5%). From the mass spectrum, infrared absorption spectrum, and ¹ H-NMR measurement results, the following formula (4
7)

[0136]

[Chemical 51]

It was confirmed to be 3- (1,1,2,2-tetrafluoroethoxy) pyromellitic acid shown in (1). [Synthesis of Fluorine-Containing Carboxylic Anhydride] 3-
(1,1,2,2-Tetrafluoroethoxy) pyromellitic acid (Chemical Formula 47) was heated and dehydrated under reduced pressure at 175 ° C. for 2 hours to obtain colorless crystals (yield 87%). It has mass spectrum, infrared absorption spectrum, and ¹ H
-From the measurement results of NMR, the following formula (48)

[0138]

[Chemical 52]

It was confirmed to be 3- (1,1,2,2-tetrafluoroethoxy) pyromellitic dianhydride as shown in.

[0140]

Example 7 Instead of bis (1,1,2,2-tetrafluoroethoxy) pyromellitic dianhydride, bis (1,1,2,2-tetrafluoroethoxy) pyromellitic dianhydride 0 .450 g (1.00 mmol) and pyromellitic dianhydride 0.218 g (1.00 mmo)
A polyimide film was obtained in the same manner as in the synthesis of the fluorine-containing polyimide of Example 1 except that the mixture of l) was used. The infrared absorption spectrum of this product is shown in FIG. The water absorption rate was 0.89%.

[0141]

Example 8 Instead of 4,4'-diaminodiphenyl ether, 3,3'-diamino-4,4'-bis (1,
1,2,2-tetrafluoroethoxy) biphenyl 0.
A polyimide film was obtained in the same manner as in the synthesis of the fluorine-containing polyimide of Example 1 except that 833 g (2.00 mmol) was used. The water absorption rate was 0.83%.

[0142]

Example 9 Bis (1,1,2,2-tetrafluoroethoxy) pyromellitic dianhydride 0.90 g (2 mmo
l) and 0.425 g of 3,3'-dimethylbenzidine (2
mmol) and 10 g of N-methylpyrrolidone were placed in a flask and stirred under a nitrogen atmosphere at room temperature for 2 days to obtain an N-methylpyrrolidone solution of polyamic acid. This was cast on a quartz substrate to form a film, which was heated and cured at 350 ° C. under nitrogen for 2 hours to obtain a polyamic acid and a polyimide film. The weight average molecular weight of this polyamic acid was 11,000. The viscosity average molecular weight of this polyimide was 8500.

[0143]

Example 10 [Synthesis of Fluorine-Containing Carboxylic Acid Tetraalkyl Ester]
Dihydroxypyromellitic acid tetraethyl ester 3.
98 g (10.0 mmol), potassium hydroxide 1.68
g (30.0 mmol), 1,4-dioxane 20 ml
Was placed in a micro-bomb having an internal volume of 100 ml and stirred at 60 ° C. for 2 hours. After the system was replaced with nitrogen gas, chlorodifluoromethane gas was introduced and the pressure was adjusted to 4.0 kg / c.
Since the pressure decreases with the progress of m ² -G, chlorodifluoromethane gas is introduced to adjust the pressure to 3.0 to 4.0 k.
The reaction was carried out for 10 hours while maintaining g / cm ² -G. After completion of the reaction, 1,4-dioxane was distilled off from the reaction solution, and water 2
0 ml was added and stirred, the organic phase was separated, and methylene chloride was distilled off to obtain white crystals. It has mass spectrum, infrared absorption spectrum, and ¹ H-N
From the MR measurement results, the following formula (49)

[0144]

[Chemical 53]

It was confirmed that this was bis (difluoromethoxy) pyromellitic acid tetraethyl ester as the target compound shown in.

[0146]

[Comparative Example 1] Except that 0.900 g (2.00 mmol) of pyromellitic dianhydride was used instead of bis (1,1,2,2-tetrafluoroethoxy) pyromellitic dianhydride. A polyimide film was obtained in the same manner as in the synthesis of the fluorine-containing polyimide of Example 1. Water absorption rate is 1.9
%Met.

[0147]

According to the present invention, a novel fluorinated carboxylic acid anhydride and a novel fluorinated polyimide having improved water absorption can be obtained from the raw material.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of bis (1,1,2,2-tetrafluoroethoxy) pyromellitic acid tetraethyl ester in Example 1.

FIG. 2 is a diagram showing an infrared absorption spectrum of bis (1,1,2,2-tetrafluoroethoxy) pyromellitic acid in Example 1.

FIG. 3 is a diagram showing an infrared absorption spectrum of bis (1,1,2,2-tetrafluoroethoxy) pyromellitic dianhydride in Example 1.

FIG. 4 is a diagram showing an infrared absorption spectrum of polyamic acid in Example 1.

FIG. 5 is a diagram showing an infrared absorption spectrum of polyimide in Example 1.

FIG. 6 is a diagram showing an infrared absorption spectrum of polyimide in Example 7.

Claims (4)

[Claims] 1. The following general formula (1): (In the formula, Z is a fluoroalkoxy group represented by Rf′O, a hydrogen atom, or a substituent or atom selected from a fluorine atom. Rf and Rf ′ are fluorine / carbon atom ratios of 1 or more and the number of carbon atoms. 1 to 12 fluorocarbon residue, which may have a chlorine atom, an ether group, or a double bond, and may be different from each other or the same one.) object. 2. The following general formula (2): (In the formula, Z is a fluoroalkoxy group represented by Rf′O, a hydrogen atom, or a substituent or atom selected from a fluorine atom. Rf and Rf ′ are fluorine / carbon atom ratios of 1 or more and the number of carbon atoms. It represents a fluorocarbon residue of 1 to 12, and may have a chlorine atom, an ether group, or a double bond, and may be different from each other or the same as each other R ¹ , R ² , R ³ , R ⁴ is a substituent or atom selected from an alkyl group having 1 to 10 carbon atoms which may have a branched structure, a hydrogen atom, an alkali metal atom, and a quaternary ammonium radical, and they are the same or different. The fluorinated carboxylic acid derivative represented by 3. The following general formula (3):(In the formula, Z¹, Z²Is a fluoro group represented by Rf'O.
Substitution selected from alkoxy group, hydrogen atom and fluorine atom
A group or atom, Z¹And Z²Is either one or
Both are fluoroalkoxy groups. Rf and Rf '
Has a fluorine / carbon atom ratio of 1 or more and 1 to 12 carbon atoms.
Represents a fluorocarbon residue of chlorine atom, ether
Group, may have a double bond, different from each other
May be the same. A is at least 2 charcoal
It is a divalent group containing an elementary atom. ) Repeated
Containing a structural unit, the weight average molecular weight is 1 × 10³~ 1
× 10 ⁷Is a fluorinated polyamic acid. 4. The following general formula (4):(In the formula, Z is a fluoroalkoxy represented by Rf′O.
Si group, a hydrogen atom, a substituent selected from a fluorine atom or
Is an atom. Rf and Rf 'are fluorine / carbon atom ratios
Is a fluorocarbon residue having 1 or more and 1 to 12 carbon atoms
Represents a chlorine atom, an ether group, or has a double bond
May be different or the same
Yes. A is a divalent group containing at least two carbon atoms
Is. ) Contains a repeating structural unit represented by
Average molecular weight is 1 × 10³~ 1 x 10 ⁷Fluorine-containing
Riimide.