JPH03137122A - Fluorine-containing polyester - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having excellent water-repellency and oil repellency by copolymerizing a specific dicarboxylic acid unit and a diol unit. CONSTITUTION:The objective polymer is produced by mixing (A) >=1 mol% of a dicarboxylic acid giving a constituent unit of formula I (X is O, CO, etc.; R<1> is fluorine-substituted 1-20C alkyl; r is 0 or 1) and (B) >=70 mol% of a diphenol giving a constituent unit of formula II (R<2> is aromatic group) (e.g. resorcinol) to (C) e.g. terephthalic acid ad ethylene glycol and carrying out the polycondensation of the composition using melt-polymerization process.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fluorine-containing polyester having water and oil repellency.

[Prior Art] Fully aromatic polyester has been known as a material with excellent heat resistance and mechanical strength.
Furthermore, existing fluoropolymers such as conventional polytetrafluoroethylene are added in order to impart water repellency, oil repellency, and sliding properties. However, this method had a problem in that the fluoropolymer and the wholly aromatic polyester were inherently incompatible, and thus a decrease in transparency was unavoidable. Furthermore, the water repellency and oil repellency also had the problem of insufficient durability.

In an attempt to overcome these problems, Japanese Unexamined Patent Publication No. 62-3
In JP 2118, a wholly aromatic polyester is synthesized using tetrafluorophthalic acid or monochlorotrifluorophthalic acid as a dicarboxylic acid component.

[Problems to be Solved by the Invention] However, the technique disclosed in JP-A-62-32118 was insufficient in terms of water and oil repellency. Due to these drawbacks, the range of use has been extremely limited.

An object of the present invention is to provide a fluorine-containing polyester with excellent water and oil repellency.

[Means for Solving the Problems] The present invention has the following configuration to achieve the above object.

"1 mol% or more of the dicarboxylic acid units are units represented by the following general formula (I), and 70 mol% or more of the diol units are units represented by the following general formula (II). fluorine-containing polyester.

-←0-R2-0→-(II) (In formulas (I) and (II), X is 10-Q
Q Ur is 0 or 1
shows. R1 represents an alkyl group having 1 to 20 carbon atoms and substituted with at least one fluorine atom. R2 represents a divalent aromatic group. )" In the present invention, R+ represents an alkyl group having 1 to 20 carbon atoms and substituted with at least one fluorine atom. The number of carbon atoms in R1 is preferably 2 or more, more preferably 3 to 10, from the viewpoint of the reactivity of dicarboxylic acid, which is a starting material for polyester, and water and oil repellency. The number of fluorine atoms substituted in R1 is preferably 2 or more from the viewpoint of water and oil repellency of the polyester,
Further, since R1 is preferably an alkyl group having 3 or more carbon atoms, the number of fluorine atoms is particularly preferably 7 or more. Further, it is preferable that the terminal alkyl group is fluorinated in order to exhibit high water and oil repellency.

R1 may be linear or branched. Further, it may contain an unsaturated bond. Specific examples where R1 is a straight chain include methyl group, ethyl group, n-propyl group, n-butyl group, n-
Examples include pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group. R
Specific examples where 1 is branched include isopropyl group, isobutyl group, 5ee-butyl group, tert-butyl group, 1
-Methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1゜2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethyl-2-methyl-1-propenyl group , 2-isopropyl-1,3-dimethyl-1-butenyl group, and the like.

Among them, specific examples of fluorinated terminal alkyl groups that exhibit high water and oil repellency include 5. 5
．． 5.4. 4. 3. Examples include 3-hebutafluoropentyl group.

The fluorine-containing polyester of the present invention contains a dicarboxylic acid component in which 1 mol% or more is a dicarboxylic acid represented by the following general formula (m), and 70 mol% or more is a diol represented by the following general formula (IV). It is manufactured by polymerizing with a diol component.

(In the formula, X, , r, R' are the same as in general formula (I), and Z
is a hydroxy group or a halogen group. )HO-R2
-OH(IV) (In the formula, R2 is the same as in general formula (II).) As a method for producing the dicarboxylic acid represented by the above general formula (I[), a dicarboxybenzene derivative and at least one fluorine Examples include a method of obtaining it by reaction with a compound containing an alkyl group substituted by an atom. Alternatively, a xylene derivative is reacted with a compound containing an alkyl group substituted by at least one fluorine atom, and then two methyl groups bonded to a phenyl group are converted into carboxyl groups using a conventionally known oxidizing agent. Further, when dihalogen is obtained, halogenation can be carried out using various conventionally known halogenating agents for carboxylic acids.

Specific examples of the dicarboxylic acid represented by the above general formula (III) include dicarboxyphenyl trifluoromethyl ether, dicarboxyphenyl difluoroethyl ether, dicarboxyphenyl trifluoroethyl ether, dicarboxyphenylpentafluoroethyl ether, Dicarboxyphenyl tetrafluoropropyl ether, dicarboxyphenyl pentafluoropropyl ether, dicarboxyphenyl hexafluoropropyl ether, dicarboxyphenyl hexafluoroisopropyl ether, dicarboxyphenyl hexafluorobutyl ether, dicarboxyphenyl nonafluoro-t
-Butyl ether, dicarboxyphenyl perfluorodecyl ether, dicarboxyphenyl octafluoropentyl ether, dicarboxyphenyl perfluoropentyl ether, dicarboxyphenyl nonafluorohexyl ether, dicarboxyphenyl perfluorohexyl ether, dicarboxyphenyl dodecafluorohexyl ether , dicarboxyphenyl tridecafluoroheptyl ether, dicarboxyphenyl perfluoroheptyl ether, dicarboxyphenyl tridecafluorooctyl ether, dicarboxyphenyl pentadecafluorooctyl ether, dicarboxyphenyl perfluorooctyl ether, dicarboxyphenyl hexafluoro Nonyl ether, dicarboxyphenyl perfluorononyl ether, dicarboxyphenyl hebutadecafluorodecyl ether, dicarboxyphenyl perfluorodecyl ether, dicarboxyphenyl perfluoro-1-ether-2-methyl-1-propenyl ether, dicarboxy Dicarboxyphenylfluoroalkyl ether such as phenylperfluoro-2-isopropyl-1,3-dimethyl-1-butenyl ether, difluoroethyl dicarboxybenzoate, trifluoroethyl dicarboxybenzoate, tetrafluoropropyl dicarboxybenzoate , pentafluoropropyl dicarboxybenzoate, hexafluoroisopropyl dicarboxybenzoate, hebutafluorobutyl dicarboxybenzoate, nonafluoro-dicarboxybenzoate
t-Butyl, octafluoropentyl dicarboxybenzoate, nonafluorohexyl dicarboxybenzoate, dodecafluorohbutyl dicarboxybenzoate, tridecafluorooctyl dicarboxybenzoate, pentafluorodecafluorooctyl dicarboxybenzoate, dicarboxy Fluoroalkyl dicarboxybenzoates such as hexadecafluorononyl benzoate, dicarboxyphenyl hebutadecafluorodecyl, N-difluoroethyldicarboxybenzamide, N-trifluoroethyldicarboxybenzamide, N-tetrafluoropropyldicarboxybenzamide , N-pentafluoropropyldicarboxybenzamide, N-hexafluoroisopropyldicarboxybenzamide, N-hebutafluorobutyldicarboxybenzamide, N-(nonafluoro-t-butyl)dicarboxybenzamide, N-octafluoropentyldicarboxy Benzamide, N-nonafluorohexyldicarboxybenzamide, N-dodecafluorohebutyldicarboxybenzamide, N-)
Ridecafluorooctyl dilupoxybenzamide, N
- N-fluoroalkyl dicarboxybenzamide such as pentadecafluorooctyl dicarboxybenzamide, N-hexadecafluorononyl dicarboxybenzamide, N-heptadecafluorodecyl dicarboxybenzamide, dicarboxyphenyl trifluoromethyl ketone, dicarboxyphenyl Pentafluoroethyl ketone, dicarboxyphenyl perfluoropropyl ketone, dicarboxyphenyl perfluorononyl ketone,
Dicarboxyphenyl perfluoropentyl ketone, dicarboxyphenyl perfluorohexyl ketone, dicarboxyphenyl perfluorohebbutyl ketone, dicarboxyphenyl perfluorooctyl ketone, dicarboxyphenyl perfluorononyl ketone, dicarboxyphenyl perfluorononyl ketone, etc. Carboxyphenylfluoroalkylketone, dicarboxytrifluoromethylbenzene, dicarboxyfluoroethylbenzene, dicarboxytrifluoroethylbenzene, dicarboxypentafluoroethylbenzene, dicarboxytetrafluoropropylbenzene, dicarboxypentafluoropropylbenzene, dicarboxyperfluoropropylbenzene , dicarboxypentafluorobutylbenzene, dicarboxyperfluorobutylbenzene, dicarboxynonafluoropentylbenzene, dicarboxyperfluoropentylbenzene, dicarboxyundecafluorohexylbenzene, dicarboxyperfluorohexylbenzene, dicarboxydodecafluoroheptylbenzene , dicarboxyperfluoroheptylbenzene, dicarboxypentadecafluorooctylbenzene, dicarboxyperfluorooctylbenzene,
Examples include dicarboxyfluoroalkylbenzenes such as dicarboxyhebutadecafluorononylbenzene, dicarboxyperfluorononylbenzene, dicarboxynonadecafluorodecylbenzene, dicarboxyperfluorodecylbenzene, and dihalides of the above dicarboxylic acids. be able to.

As the dicarboxylic acid component of the present invention, the general formula (I
It is necessary to contain the dicarboxylic acid represented by II) in an amount of 1 mol % or more, so that water and oil repellency can be exhibited, and the content is preferably 5 mol % or more. Other dicarboxylic acid components are not particularly limited, and include, for example, the following dicarboxylic acids, and their dichlorides, difluorides, and dibromides. Namely, terephthalic acid, tetrafluoroterephthalic acid, isophthalic acid, tetrafluoroisophthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5
-naphthalene dicarboxylic acid, 2゜6-naphthalene dicarboxylic acid, 4.4'-diphenyl ether dicarboxylic acid, 3. 3'-diphenyl ether dicarboxylic acid, 4
．． 4'-diphenylmethanedicarboxylic acid, 3,3'
-diphenylmethane dicarboxylic acid, 4. 4'-diphenylsulfonedicarboxylic acid, 3.3'-diphenylsulfonedicarboxylic acid, 2,2-bis(carboxyphenyl)propane, 2,2-bis(carboxyphenyl)
Aromatic dicarboxylic acids such as hexafluoropropane, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid, succinic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid Examples include aliphatic dicarboxylic acids such as acids, and their dichlorides, difluorides, and dibromides.

However, in the present invention, the number of fluorine atoms in R1 is 12
In the above case, when the dicarboxylic acid represented by the general formula (III) in the dicarboxylic acid component exceeds 50 mol %, the solubility of the polyester in the organic solvent tends to decrease.

In the above general formula (IV), R2, which is a divalent aromatic residue, is particularly preferably a mono- to tetranuclear body.

Specific examples of the diphenol represented by the general formula (IV) include catechol, 4-
Catechols such as methylcatechol, 4-t-butylcatechol, 4-phenylcatechol, resorcinol, 4-
Resorcinols such as methylresorcinol, 4-t-butylresorcinol, 4-phenylresorcinol, hydroquinone,
Hydroquinones such as 2-methylhydroquinone, 2-t-butylhydroquinone, and 2-phenylhydroquinone; examples where R is a dinuclear substance include 2°2'-dihydroxybiphenyl; 4. 4'-dihydroxybiphenyl, 3.3', 5.5'-tetramethyl-4,4'
-dihydroxybiphenyl, 3.3', 5.5'-tetrachloro-4,4'dihydroxybiphenyl, 3.3
Examples of dihydroxybiphenyls such as ', 5,5'tetrabromo-4,4'-dihydroxybiphenyl, and bis(hydroxyphenyl)alkane skeletons include 4.
4'-dihydroxydiphenylmethane, 3°3'5.5
'-Tetramethyl-4,4'-dihydroxydiphenylmethane, 3.3',5.5'-tetrachloro-4,4
'-dihydroxydiphenylmethane, 3. 3',
5. Dihydroxydiphenylmethanes such as 5'-tetrabromo-4,4'-dihydroxydiphenylmethane, bis(4-hydroxyphenyl)diphenylethane, bis(3°5-dimethyl-4-hydroxyphenyl)diphenylethane, bis(3,5- dichloro-4-hydroxyphenyl)diphenylethane, bis(3゜5-
Bis(hydroxyphenyl)ethanes such as dibromo-4-hydroxyphenyldiphenyl)ethane, 2.2-
Bis(4-hydroxyphenyl)propane, 2,2'-
Bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl) ) propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)hexafluoropropane, 2゜2-bis(3,
Bis(5-dichloro-4-hydroxyphenyl)hexafluoropropane, 2,2nibis(3,5-dibromo-4-hydroxyphenyl)hexafluoropropane, etc.
hydroxyphenyl)propanes, 2,2-bis(4-
hydroxyphenyl)butane, 2,2-bis(3,5-
dimethyl-4-hydroxyphenyl)butane, 2゜2-
Bis(hydroxyphenyl)butanes such as bis(3,5-dichloro-4-hydroxyphenyl)butane, 2,2
-bis(3,5-dibromo-4-hydroxyphenyl)
Butane, 3,3-bis(4-hydroxyphenyl)pentane, 3,3-bis(3,5-dimethyl-4-hydroxyphenyl)pentane, 3,3-bis(3,5-dichloro-4-hydroxyphenyl) ) pentane, bis(hydroxyphenyl)pentanes such as 3,3-bis(3,5-dibromo-4-hydroxyphenyl)pentane, 1,1
Bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-1-phenylethane, 1,1-bis(3,5
Bis(hydroxyphenyl)phenylethanes such as -dichloro-4-hydroxyphenyl)-1-phenylethane, 1,1-bis(3,5-dibromo-4-hydroxyphenyl)-1-phenylethane, bis(hydroxyphenyl)-1-phenylethane, As an example having a phenyl) heteroatom skeleton, 4. 4'
-dihydroxydiphenyl ether, 3.3'
5.5'-tetramethyl-4,4'-dihydroxydiphenyl ether, 3.3'5.5'-tetrachloro-4
, 4' dihydroxy diphenyl ether, 3. 3'
, 5. Dihydroxydiphenyl ethers such as 5'-tetrabromo-4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 3°3', 5,5'-tetramethyl-4,4'-
Dihydroxydiphenyl sulfone, 3.3', 5.5'
-tetrachloro-4,4'-dihydroxydiphenylsulfone, 3.3',5.5'-tetrabromo-4,
Dihydroxydiphenyl sulfones such as 4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl) sulfide, bis(3°5-dimethyl-4-hydroxyphenyl) sulfide, bis(3,5-dichloro-4
Hydroxyphenylsulfides such as -hydroxyphenyl) sulfide and bis(3,5-dibromo-4-hydroxyphenyl) sulfide; diphenols having skeletons other than those mentioned above include 9-bis(4-hydroxyphenyl)fluorene, 3 - (4-1 hydroxyphenyl)
-1,1,3-)rifthyl-5-indanolphenolphthalein, 1,4-naphthalenediol, 1,5-
naphthalene diol, 2,6-naphthalene diol, 2
, 7-naphthalenediol, and 1,2-bis(4-hydroxybenzoyloxy)ethane.

In the present invention, in order to sufficiently increase the glass transition temperature, it is necessary to contain 70 mol% or more of these aromatic diols, but it is also possible to use aliphatic diols in the other less than 30 mol%. It is possible. Usable aliphatic diols include ethylene glycol, propylene glycol, trimethylene glycol, butane 1
．． 3-diol, 2,2-dimethylpropane 1,3-diol, 2,2-dimethylpropane 1,3-diol,
Examples include 2-butene 1,4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, heptamethylene glycol, and cyclohexane dimetatool.

The method for producing the polyester of the present invention includes, for example, dissolving the above dicarboxylic acid (or dicarboxylic acid cibarabide) in an organic solvent that is not compatible with water, and mixing and reacting this with diphenol dissolved in an alkaline aqueous solution. Polymerization method (see Japanese Patent Publication No. 40-1959), solution polymerization method (Japanese Patent Publication No. 37-1973) in which dicarboxylic acid (or dicarboxylic acid civalide) and diphenol are reacted in an organic solvent.
5599). In addition, there is a method of polymerizing dicarboxylic acid diphenyl ester and a biphenol compound in a molten state (Japanese Patent Publication No. 38-115247
No. 43-28119), a method of polymerizing an aromatic dicarboxylic acid and an acetate of a biphenol compound in a molten state [Industrial and E.
ngineering Chemisfr7 Vol.
51 p. 47 (1959).

At this time, usual catalysts, stabilizers such as phosphorous acid, phosphoric acid or derivatives thereof, phenol derivatives, etc. may be used as necessary.

The molecular weight of the polyester of the present invention thus produced is limited by the amounts of the dicarboxylic acid or dicarboxylic acid civalide represented by the above general formula (III) and the biphenol compound represented by the above general formula (IV). A preferable molecular weight is 0.1 to 2.0% in terms of intrinsic viscosity, in terms of the ability to form fibers, films, and three-dimensional products, and the physical properties of the resulting fibers, films, and three-dimensional products.
Odl/H, preferably 0.2 to 1.5 dl/H.

In addition, it can be formed by conventional melt forming methods such as extrusion molding, injection molding, compression molding, and blow molding, and can be processed into fibers, films, three-dimensional molded products, containers, hoses, etc. be.

Moreover, the polyester of the present invention becomes soluble in all or part of solvents such as chloroform, benzene, N,N-dimethylformamide, N-methyl-2-pyrrolidone, cresol, 0-chlorophenol, and tetrahydrofuran. Therefore, it is also possible to use the solution by forming it into a solution using an appropriate solvent and then coating it on a substrate such as a glass plate.

The fluorine-containing polyester of the present invention is also useful as a resin component for water-repellent paints.

[Example] Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 0.57 g (
2.2-bis(4-hydroxyphenyl)propane (2.5 mmol) and 15 μm of benzyltriethylammonium chloride were dissolved. To this, 0.16 g (0.25 mmol) dissolved in 5.0 ml dichloromethane was added.
) of 5-[[3,4,4,4-tetrafluoro-2-
[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-1,3-bis(trifluoromethyl)-1-butenyl]oxycoisophthaloyl dichloride, 0°20g (1,0m mol) of isophthaloyl dichloride, 0.38 g (1,25 mm mol) of terephthaloyl dichloride were added in one portion, and 10
Stirred at °C for 30 minutes. The reaction solution was poured into 300 ml of boiling water to which a small amount of hydrochloric acid was added to obtain a white flaky polymer.

Yield: 98% Intrinsic viscosity: 0°84 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
．． Measured at a concentration of 5 g/dl) Infrared absorption spectrum (KB
r) cm 1750 (C=O) 1200 (C-F) The generated polymer was 1. 1. 2. Dissolved in 2-tetrachloroethane and spread the solution on a glass plate. This is 80℃
Heat for 6 hours and 1. 1. 2. After evaporating 2-tetrachloroethane, it was vacuum dried for 2 days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact: 101° Deccan contact angle = 20° Various performances are shown in Table 1.

Example 2 0.57 g (
2.5 m mat) of 2,2-bis(4-hydroxyphenyl)propane and 15 m of benzyltriethylene ammonium chloride were dissolved. To this, add 0.32 g (0.5 m m
ol) of 5-[[3,4,4゜4-tetrafluoro-
2-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-1,3-bis(trifluoromethyl)-1-butenyl]oxy]isophthaloyl dichloride, 0.15 g ( 0.75 mmol) of isophthaloyl dichloride, 0.75 mmol) of isophthaloyl dichloride; 38g (1,25m mo
The mixture of terephthaloyl dichloride (1) was added all at once, and the mixture was stirred at 10°C for 30 minutes. The reaction solution was poured into 300 ml of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield: 97% Intrinsic viscosity: 0. 83 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
1.1.
2. Dissolved in 2-tetrachloroethane and spread the solution on a glass plate. This was heated at 80°C for 6 hours and 1.1, 2.
After evaporating 2-tetrachloroethane, it was vacuum dried for 2 days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact angle: 104° Deccan contact angle 230° Various performances are shown in Table 1.

Example 3 0.84 g in 5.1 ml of LM-NaO'H aqueous solution
(2.5 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 15 μm of benzyltriethylammonium chloride were dissolved. To this, 0.32 dissolved in 5.0 ml of dichloromethane
g (0,50 mmol) of 5-[[3,4,4,4
-tetrafluoro-2-[1゜2.2.2-tetrafluoro-1-(trifluoromethyl)ethyl]-1,3-
bis(trifluoromethyl)-1-butenyl]oxy]
Isophthaloyl dichloride, 0. 86g (2.0m
mol) of 2.2-bis(chlorocarbonylphenyl)hexafluoropropane was added all at once, and 10
The mixture was stirred at ℃ for 30 minutes. The reaction solution was mixed with a small amount of hydrochloric acid.
00 ml of boiling water to obtain a white flaky polymer.

Yield: 97% Intrinsic viscosity: 0. 65 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
．． The polymer measured at a concentration of 5 g/dl was 1. 1. 2. Dissolved in 2-tetrachloroethane and spread the solution on a glass plate. This is 80℃
Heat for 6 hours and 1. 1. 2. After evaporating 2-tetrachloroethane, it was vacuum dried for 2 days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact angle = 105° Deccan contact angle: 31° Various performances are shown in Table 1.

Example 4 To 5.1 ml of IM-NaOH aqueous solution, 0.63 g (
2.5 mmol) of 2,2-bis(4-hydroxyphenyl)sulfone was dissolved in 15 μm of benzyltriethylammonium chloride. To this, add 0.26 g (0.50 mm) dissolved in 5.0 ml of dichloromethane.
of) 5-tridecafluorohexylisophthaloyl dichloride, 0.55 g (2, Om mol) of 2.
A mixture of 4.5.6-titrafluoroisophthaloyl dichloride was added at once and stirred at 10°C for 30 minutes. The reaction solution was poured into 300 ml of boiling water to which hydrochloric acid was added to obtain a white flaky polymer.

Yield: 95% Intrinsic viscosity: 0. 30 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
．． (measured at a concentration of 5 g/di). 1.
2. Dissolved in 2-tetrachlorethane and spread the solution on a glass plate. This was heated at 80°C for 6 hours, and 1.
1. 2. After evaporating the 2-tetrachloroethane,
It was vacuum dried for 2 days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact angle = 105° Deccan contact angle: 34° Various performances are shown in Table 1.

Example 5 To 5.1 ml of LM-NaOH aqueous solution, 0.50 g (2
, 5 mmol) of 2,2-bis(4-hydroxyphenyl)ethane and 15 μm of benzyltriethylammonium chloride were dissolved. To this, 0.19g (0.50m mol) dissolved in 5.0ml dichloromethane
A mixture of 5-hebutafluoropropylisophthaloyl dichloride and 0.37 g (20 mmol) of adipoyl dichloride was added at once, and the mixture was stirred at 10°C for 30 minutes. The reaction solution was poured into 300 ml of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield: 95% Intrinsic viscosity: 0. 30 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
．． (measured at a concentration of 5 g/+II). 1
．． 2. Dissolved in 2-tetrachloroethane and spread the solution on a glass plate. Heat this at 80°C for 6 hours and 1.
1. 2. After evaporating the 2-tetrachloroethane,
It was vacuum dried for 2 days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact angle: 98° Deccan contact angle = 18° Various performances are shown in Table 1.

Comparative Example 1 0.57 g (
2.5 mmol of 2,2-bis(4-hydroxyphenyl)propane and 15 μm of benzyltriethylammonium chloride were dissolved. To this, 0.38 g (1.25 m
+1101) isophthaloyl dichloride, 0.38g
A mixture of (1.25 m not) of terephthaloyl dichloride was added at once and stirred at 10°C for 30 minutes. The reaction solution was poured into 300 ml of boiling water to which a small amount of hydrochloric acid was added to obtain a white flaky polymer.

Yield: 97% Intrinsic viscosity: 0. 90 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
．． (measured at a concentration of 5 g/dl). 1.
2. Dissolved in 2-tetrachloroethane and spread the solution on a glass plate. Heat the slices at 80℃ for 6 hours.1. 1
．． 2. After evaporating 2-tetrachloroethane, 2
Vacuum dried for several days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact angle: 83° Deccan contact angle is 20.

Various performances are shown in Table 1.

Comparative Example 2 0.84 g (
2.5 mmol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane and 15 μm of benzyltriethylammonium chloride were dissolved. to this,
Dissolved in 5.0 ml of dichloromethane. 1. 07g
(2.5 mmol) of 2,2-bis(chlorocarbonylphenyl)hexafluoropropane was added at once and stirred at 10°C for 30 minutes. The reaction solution was poured into 300 ml of boiling water to which a small amount of hydrochloric acid was added to obtain a white flaky polymer.

Yield: 96% Intrinsic viscosity: 0. 75 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
．． The resulting polymer was dissolved in 1.1,2.2-tetrachloroethane and the solution was spread on a glass plate. Heat this at 80°C for 6 hours and 1. 1. 2. After evaporating 2-tetrachloroethane, it was vacuum dried for 2 days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact angle = 95° Deccan contact angle 20.

Various performances are shown in Table 1.

Comparative Example 3 0.63 g (
2.5 mmol) of 2,2-bis(4-hydroxyphenyl)sulfone and 15 μm of benzyltriethylammonium chloride were dissolved. To this, 0.69 g (2.5 mmol) dissolved in 5.0 ml dichloromethane
2.4. 5. A mixture of 6-titrafluoroisophthaloyl dichloride was added at once and stirred at 10°C for 30 minutes. The reaction solution was poured into 300 ml of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield: 95% Intrinsic viscosity: 0. 25 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
．． (measured at a concentration of 5 g/di). 1. 2. Dissolved in 2-tetrachloroethane and spread the solution on a glass plate. This is 80℃
Heat for 6 hours and 1. 1. 2. After evaporating 2-tetrachloroethane, it was vacuum dried for 2 days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact angle: 86° Deccan contact angle 20.

Various performances are shown in Table 1.

Comparative Example 4 To 5.1 ml of IM-N a OH aqueous solution, add 0.5
0 g (2.5 mmol) of 2,2-bis(4-hydroxyphenyl)ethane and 15 μm of benzyltriethylammonium chloride were dissolved. In addition, 5.0m
0.46 g (2.5 m
mol) of adipoyl dichloride was added at once and stirred at 10°C for 30 minutes. The reaction solution was poured into 300 ml of boiling water to which a small amount of hydrochloric acid had been added to obtain a white flaky polymer.

Yield: 94% Intrinsic viscosity: 0. 33 dl/g (in 1,1,2,2-tetrachloroethane, 25°C, 0
．． (Measured at a concentration of 5 g/dl) The produced polymer was 1. 1. 2. Dissolved in 2-tetrachloroethane and spread the solution on a glass plate. This is 80℃
Heat for 6 hours and 1. 1. 2. After evaporating 2-tetrachloroethane, it was vacuum dried for 2 days. The contact angles of water and decane on the surface of the obtained glass plate were measured.

Water contact angle = 78° Deccan contact angle 206 Various performances are shown in Table 1.

Table 1 [Effects of the Invention] According to the present invention, it was possible to provide a fluorine-containing polyester having excellent water repellency and oil repellency.

Claims (1)

[Claims] (1) 1 mol% or more of the dicarboxylic acid units are units represented by the following general formula (I), and 70 mol% or more of the diol units are units represented by the following general formula (II). A fluorine-containing polyester characterized by ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In formulas (I) and (II), X is -O-, ▲mathematical formula,
Choose from ▼, ▲ ▲ ▼ ▲ ▲ ▲ ▲ ▲ ▼ ▼ ▲ ▲ ▼ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ ▲ R^1 represents an alkyl group having 1 to 20 carbon atoms and substituted with at least one fluorine atom. R^2 represents a divalent aromatic group. )