JP2003012601A - Alicyclic fluorine-containing dicarboxylic acid and polymer by using the same or composition for photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new alicyclic fluorine-containing dicarboxylic acid or its derivative, further a polymer by using the above alicyclic fluorine-containing dicarboxylic acid and an acid-instable compound for achieving a low dielectric property and high transparency, and among them, to provide a fluorine- containing polybenzoxazole as a low dielectric polymer equipped with a high heat resistance, or a fluorine-containing polyhydroxyamide as its precursor. SOLUTION: This fluorine-containing polymer is obtained by polymerizing a fluorine-containing dicarboxylic acid expressed by the formula (1), or its amide-forming compound or ester-forming derivative.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel alicyclic fluorinated dicarboxylic acid or a derivative thereof, and further to a polymer using the alicyclic fluorinated dicarboxylic acid or a derivative thereof. In particular, fluorine-containing polybenzoxazole or a fluorine-containing polyhydroxyamide which is a precursor thereof, a coating composition in which a polymer thereof is dissolved in an organic solvent, or the alicyclic fluorine-containing dicarboxylic acid is acid-labile group-ized. Regarding compounds and the like.

[0002]

BACKGROUND OF THE INVENTION Generally, dicarboxylic acids are polyesters,
It is used as a monomer for condensation or addition polymerization of polyamide, urethane resin, epoxy resin, polybenzoxazole and the like. Since the obtained polymer mainly has a cyclic structure in the molecule, it has many mechanical strengths such as high mechanical strength such as tensile strength and bending strength, and excellent thermal stability such as thermal decomposition temperature and thermal deformation temperature. is there. In particular, polybenzoxazole is positioned as a high-performance engineering plastic along with polyimide. Its basic skeleton and manufacturing method are known from Japanese Examined Patent Publication No. 42-19271.

These resins are used in various applications such as engineering plastics, heat resistant coating materials, electronic materials, electronic component materials, and optical materials. Especially, assuming that they are used as semiconductors and optical members, communication equipment will be used. Since the needs for high-speed processing, high-frequency applications, etc. are increasing with the development of, as a result, low dielectric constant and high transparency are required. It is also important to have a low coefficient of thermal expansion. As a means for imparting such a low dielectric constant and a means for imparting high transparency, fluoropolymers which reduce electron density have been actively studied.

From the viewpoint of a polymer having high heat resistance,
Since polybenzoxazole has a cyclic structure that does not have a carbonyl group compared to polyimide, it is expected that the polarization will be small and the dielectric constant will be low. For example, polybenzoxazole containing fluorine will have a dielectric constant lower than that of polyimide. Will also be significantly smaller. At the same time, the introduction of fluorine has been reported in polybenzoxazole containing fluorine to improve water resistance and enhance new functionality such as optical and electrical properties (JP-A-62-207332, JP-A-62-332332). 3-290434, etc.).

However, although the conventional fluorine-containing polybenzoxazole has a considerably lowered dielectric constant, it is not sufficiently adaptable to future semiconductor applications that will continue to progress. In terms of transparency, from an application point of view, for example, in the photoresist field, the F ₂ laser wavelength (157 nm) from the ultraviolet region to vacuum ultraviolet rays is used.
Up to the above, high transparency in a wide wavelength range is required depending on the application, but a wholly aromatic type fluoropolymer cannot exhibit sufficient transparency. On the other hand, in the field of optical waveguides, high transparency at a communication wavelength of 1.55 microns is also required.

[0006]

DISCLOSURE OF THE INVENTION In order to achieve low dielectric properties and high transparency, the present invention provides a novel alicyclic fluorine-containing dicarboxylic acid or derivative thereof, and further the alicyclic fluorine-containing dicarboxylic acid or its derivative. It is an object to provide a polymer using a derivative and an acid labile compound. Above all, a fluorine-containing polybenzoxazole or a fluorine-containing polyhydroxyamide which is a precursor thereof is provided as a low dielectric polymer having high heat resistance.

[0007]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the inventors of the present invention have made earnest studies on the development of a new dicarboxylic acid, and as a result, a new monomer having a fluorine atom and an alicyclic group introduced into the molecule. The present invention has been accomplished and various investigations have been made on the polymer to realize the unprecedented reduction in dielectric constant and improvement in transparency, and the present invention has been completed.

That is, the present invention is 1. It is a fluorine-containing dicarboxylic acid represented by the formula (1).

[0009]

[Chemical 5]

2. Further, the present invention is a fluorine-containing polymer polymerized by using the general formula (1) or its amide-forming derivative or ester-forming derivative. 3. In addition, the present invention provides the general formula (2),

[0011]

[Chemical 6]

(In the formula, X is a tetravalent organic group containing an aromatic ring, and two sets of N and O are bonded to the aromatic ring of X in the ortho position to form a five-membered ring. ) Is a fluorine-containing polybenzoxazole containing a structural unit represented by. 4. In addition, X is the general formula (3),

[0013]

[Chemical 7]

(In the formula, each aromatic ring has a dangling bond at the ortho position, and the hydrogen atom of the aromatic ring may be substituted with halogen (fluorine, chlorine, bromine and iodine)). Is a fluorine-containing polybenzoxazole of the above-mentioned general formula (2) which is an organic group. 5. Further, the present invention provides the general formula (4),

[0015]

[Chemical 8]

A fluorine-containing polyhydroxyamide represented by the formula (wherein X is the same as X in the general formula (2)). 6. Moreover, it is a composition for coating which melt | dissolved the polymer in any one of said 2-4 in the organic solvent. 7. Further, it is a composition for a photosensitive material, which is obtained by modifying at least one carboxylic acid of the dicarboxylic acid represented by the general formula (1) described above with an acid labile group.

The present invention relates to an alicyclic fluorine-containing dicarboxylic acid represented by the formula (1), that is, 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane and its application.

[0018]

[Chemical 9]

Further, it relates to a polymer or an acid labile compound obtained by using the dicarboxylic acid represented by the general formula (1) as a starting material. The method for producing 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane of the general formula (1) that can be used in the present invention is not particularly limited, but 2,2-bis (which is an aromatic compound is simply used. It can be produced by using 4-carboxyphenyl) -hexafluoropropane as a raw material and introducing hydrogen at low pressure to high pressure in the presence of an organic solvent and a catalyst. In this case, a general ring hydrogenation method is preferably applied.

Further, the polymer according to the present invention is produced by using 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane represented by the general formula (1) or a derivative thereof. But not limited to
Examples of the copolymers include polyesters, polyamides, urethane resins, epoxy resins, polyketones, polybenzoxazoles and their precursors such as polyhydroxyamides, and polyamideimides and polyesterimides, which are used in combination with several condensation reactions of these. Among them, polybenzoxazole can be expected to have a wide range of applications as electronic materials and optical materials having high heat resistance.

The method for producing the fluoropolymer of the present invention is not limited, but the following formula

[0022]

[Chemical 10]

An acid component containing an amide or an ester-forming derivative synthesized from 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane or its dicarboxylic acid represented by It is polymerized by a mechanism such as condensation, addition polymerization and polyaddition with a counter monomer capable of reacting with a group. Therefore, when synthesizing a polyester, a diol compound is used as a counter monomer, when synthesizing a polyamide, a diamine compound is used as a counter monomer, and when synthesizing a urethane resin, a diisocyanate or a diol compound is used as a counter monomer, When synthesizing an epoxy resin, a diglycidyl compound is used as a counter monomer. The structures of these counter-monomers that can be used in the present invention are not particularly limited, and known compounds can be used.

As long as the alicyclic fluorine-containing dicarboxylic acid of the formula (1) or its amide-forming derivative used for producing the fluorine-containing polybenzoxazole of the present invention is used, the other acid component or its amide is used. It is also possible to copolymerize the forming derivative. That is, as the dicarboxylic acid compound that can be used in combination, oxalic acid, malonic acid,
Aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, 3,
3'-dicarboxyl diphenyl ether, 3,4'-
Dicarboxyl diphenyl ether, 4,4'-dicarboxyl diphenyl ether, 3,3'-dicarboxyl diphenylmethane, 3,4'-dicarboxyl diphenylmethane, 4,4'-dicarboxyl diphenylmethane, 3,3'-dicarboxyl diphenyldifluoromethane 3,4'-dicarboxyldiphenyldifluoromethane, 4,4'-dicarboxyldiphenyldifluoromethane, 3,3'-dicarboxyldiphenylsulfone, 3,4'-dicarboxyldiphenylsulfone,
4,4'-dicarboxyldiphenyl sulfone, 3,
3'-dicarboxyl diphenyl sulfide, 3,4 '
-Dicarboxyl diphenyl sulfide, 4,4'-dicarboxyl diphenyl sulfide, 3,3'-dicarboxyl diphenyl ketone, 3,4'-dicarboxyl diphenyl ketone, 4,4'-dicarboxyl diphenyl ketone, 2,2- Bis (3-carboxyphenyl) propane, 2,2-bis (3,4'-dicarboxyphenyl) propane, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) Hexafluoropropane, 2,2-bis (3,4 '
-Dicarboxyphenyl) hexafluoropropane,
2,2-bis (4-carboxyphenyl) hexafluoropropane, 1,3-bis (3-carboxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 1,4-bis (4-carboxy) Phenoxy) benzene, 3,3 '-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 3,4'-
(1,4-phenylenebis (1-methylethylidene))
Bisbenzoic acid, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisbenzoic acid, 2,2-bis (4- (3-carboxyphenoxy) phenyl) propane, 2,2-bis (4- (4-carboxyphenoxy) phenyl) propane, 2,2-bis (4- (3-carboxyphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-carboxyphenoxy))
Phenyl) hexafluoropropane, bis (4- (3-
Carboxyphenoxy) phenyl) sulfide, bis (4- (4-carboxyphenoxy) phenyl) sulfide, bis (4- (3-carboxyphenoxy) phenyl) sulfone, bis (4- (4-carboxyphenoxy) phenyl) sulfone, 5 -(Perfluorononenyloxy) isophthalic acid, 4- (perfluorononenyloxy) phthalic acid, 2- (perfluorononenyloxy)
Dicarboxylic acids containing a perfluorononenyloxy group such as terephthalic acid, 4-methoxy-5- (perfluorononenyloxy) isophthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) Aromatic dicarboxylic acids such as dicarboxylic acids containing a perfluorohexenyloxy group such as phthalic acid, 2- (perfluorohexenyloxy) terephthalic acid, and 4-methoxy-5- (perfluorohexenyloxy) isophthalic acid can be exemplified.

Examples of the amide-forming derivative of dicarboxylic acid used for producing the fluorine-containing polybenzoxazole of the present invention include dihalides of the dicarboxylic acid, acid halides such as dibromide, dimethyl ester and diethyl ester of the dicarboxylic acid. And the like dialkyl ester and the like.

The polybenzoxazole is represented by the general formula (2),

[0027]

[Chemical 11]

(In the formula, X is a tetravalent organic group containing an aromatic ring, and two sets of N and O are bonded to the aromatic ring of X in the ortho position to form a five-membered ring. ) Fluorine-containing polybenzoxazole containing a structural unit represented by the formula (4) and its precursor (4),

[0029]

[Chemical 12]

A fluorine-containing polyhydroxyamide represented by the formula (wherein X is the same as X in the general formula (2)).

The fluorinated polybenzoxazole of the present invention is a polymer which comprises a structural unit represented by the general formula (2) or has a structural unit of 1 to 100 mol%.
When the constitutional unit represented by the general formula (2) is 1 mol% or less, the dielectric constant of the film obtained therefrom is not sufficiently low, which is not preferable.

X in the general formula (2) includes an aromatic ring-containing 4
The structure is not particularly limited as long as it is a valent organic group,

[0033]

[Chemical 13]

Alternatively, the groups represented by the following general formula can be exemplified.

[0035]

[Chemical 14]

Here, each Y in the formula is independently a single bond, --O--, --S--, --SO _2- , --CO--, --CH.
_{2 -, - C (CH 3} ) 2 -, - CF 2 -, - C (CF 3) 2 -
And m and n are each an integer of 0 to 3. The benzene ring in these general formulas may be appropriately substituted with a lower alkyl group or a halogen atom such as chlorine, bromine or fluorine. Here, it is particularly preferable that m is 0 and n is 1, and examples thereof include the substituents represented by the following general formula (3). The benzene ring in these general formulas may be appropriately substituted with a lower alkyl group or a halogen atom such as chlorine, bromine or fluorine.

[0037]

[Chemical 15]

On the other hand, as a countermonomer in the case of synthesizing polybenzoxazole, the general formula (5),

[0039]

[Chemical 16]

(In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen or a trialkylsilyl group, and X is the same as in the general formula (2).) (Aminophenol) compounds are preferably used. That is, the precursor obtained by the reaction, that is, the general formula (2),

[0041]

[Chemical 17]

Polybenzoxazole is obtained by subjecting the fluorine-containing polyhydroxyamide represented by the formula (wherein X is the same as X in the general formula (2)) to a ring-closing reaction.

In this case, as the amide-forming derivative that can be used, an acid halide such as dichloride or dibromide of the dicarboxylic acid, or a dialkyl ester such as dimethyl ester or diethyl ester of the dicarboxylic acid can be used. The fluorine-containing polybenzoxazole of the present invention includes 2,2-bis- (4-carboxycyclohexyl)
Hexafluoropropane or an amide-forming derivative thereof is preferably about 5 to 100% of the total dicarboxylic acid used, and if it is less than 5%, the dielectric constant is not sufficiently lowered and the water absorption is also increased, which is not preferable.

Next, the fluorine-containing polybenzoxazole of the present invention will be described. Specific examples of the bis (aminophenol) -based compounds that can be used as a counter monomer with 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane or its amide-forming derivative in the fluorine-containing polybenzoxazole of the present invention are illustrated. Then, 2,4-diamino-1,5-benzenediol,
3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-diamino-4,4'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl)
Ketone, bis (3-amino-4-hydroxyphenyl)
Sulfide, bis (3-amino-4-hydroxyphenyl) ether, bis (3-hydroxy-4-aminophenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, bis (3-hydroxy-4-aminophenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis ( 3-hydroxy-4-aminophenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) difluoromethane and the like can be mentioned, and further CF ₂ and C as X in the general formula (5).
Various aminophenol compounds containing at least F ₃ can also be used. Of these, in order to efficiently realize a decrease in dielectric constant and an improvement in water resistance, the bis (aminophenol) compound represented by the general formula (5) has a hexafluoroisopropylidene group in X. Compounds such as general formula (3),

[0045]

[Chemical 18]

(In the formula, each aromatic ring has a dangling bond at the ortho position, and the hydrogen atom of the aromatic ring may be substituted with halogen (fluorine, chlorine, bromine and iodine)). Compounds having an organic group are preferred.

Among the bis (aminophenol) compounds represented by the above general formula (5), R ¹ , R ² ,
A trialkylsilyl compound of a bis (aminophenol) compound in which R ³ and R ⁴ are each represented by a trialkylsilyl group can also be used for the purpose of increasing the polymerization reactivity. These bis (aminophenol) compounds are macromolecules (M
acromolecules, vol. 21, p. 2305 (1
(1988) can be adjusted according to the method for producing 3,3′-bis (trimethylsiloxy) -4,4′-bis (trimethylsilylamino) biphenyl as shown below. For example, 3,4'-diamino-3,3'-dihydroxybiphenyl in tetrahydrofuran solution is reacted with trialkylsilyl chloride in the presence of triethylamine to give 3,3'-bis (trialkylsiloxy).
It is possible to obtain -4,4'-bis (trialkylsilylamino) biphenyl.

The fluorine-containing polybenzoxazole of the present invention and the fluorine-containing polyhydroxyamide which is a precursor thereof can be produced by reacting the acid component with the aminophenol compound. This polymerization method,
The conditions are not particularly limited. For example, a method in which an acid component and an aminophenol component are mutually dissolved (melted) at 150 ° C or higher and reacted without a solvent, an acid component and an aminophenol component are heated in an organic solvent or polyphosphoric acid at high temperature (preferably 150 ° C or higher). By the method of reacting with, a polybenzoxazole which is almost or completely ring-closed is obtained. In addition, the acid component and the aminophenol component are -20 to 8
A method of obtaining a precursor fluorine-containing polyhydroxyamide represented by the general formula (4) which is not ring-closed or only partially ring-closed by reacting in an organic solvent at a temperature of 0 ° C. Adopted. When inorganic salts or bases such as lithium chloride or calcium chloride are added to the polymerization reaction system, the intramolecular hydrogen bond of the aminophenol component is suppressed, and the acidic component and the amino group of aminophenol are selectively reacted to polymerize. Reactivity can also be increased.

The fluorine-containing polyhydroxyamide or the partially ring-closed fluorine-containing polyhydroxyamide which is a precursor has a temperature of 100 ° C. or higher, preferably 150 ° C. or higher,
If necessary, an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride, a ring-closing agent such as dicyclohexylcarbodiimide, and a ring-closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, or imidazole are appropriately added to close the ring. As a result, polybenzoxazole can be obtained.

The organic solvent that can be used in the polymerization reaction of the fluoropolymer according to the present invention is not particularly limited as long as both components of the raw materials are dissolved, but N, N-dimethylformamide,
N, N-dimethylacetamide, dimethylsulfoxide, phenol, o-cresol, N-methyl-2-pyrrolidone, sulfolane, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, γ
-Butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α
-Methyl-γ-butyrolactone, ethylene carbonate, propylene carbonate, triethylene glycol, acetophenone, 1,3-dimethyl-2-imidazolidinone and the like can be used. Further, as long as the solubility of both raw material components is not impaired, other organic solvents, for example, butyl acetate, ethyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl acetate, acetic acid. Butyl, isobutyl acetate, dibutyl ether, diethylene glycol dimethyl ether,
Propylene glycol methyl acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpenes, mineral spirits, petroleum naphtha-based solvents, etc. It can be used without doing.

When a dihalide is used as an acid component in these polymerization reactions, an amine-based halogen trapping agent such as pyridine, toethylamine and dimethylaniline can be used.

When the above-mentioned trialkylsilyl group-containing component is used, a polymer containing a trialkylsilyl group is obtained after polymerization. In this case, the polymer is added to methanol or water to add the trialkylsilyl group. It can be converted into an OH group.

Each of the fluoropolymers according to the present invention, which is soluble in dimethylacetamide, is dissolved in the solvent at a concentration of 0.1 g / dl, and the reduced viscosity measured at 30 ° C. by an Ostwald viscometer is 0. It is preferably 0.01 dl / g or more, particularly 0.3 dl / g or more.

The fluoropolymer of the present invention can be used in a varnish state dissolved in an organic solvent, a powder state, a film state or a solid state. When used in varnish, glass, silicon wafer, metal, metal oxide, ceramics, spin coating on a substrate such as resin,
It can be applied by a commonly used method such as spray coating, flow coating, impregnation coating, and brush coating. Since this precursor has a phenolic acidic group in its molecule and is soluble in alkali water, it is necessary to protect the phenolic hydroxy group of this precursor with an acid labile group or an amine labile group in advance, or to use light or electron beams. By introducing a functional group capable of reacting and curing with X-rays, etc., it can be used as a positive or negative resist or a photosensitive material. For example, when it is used as a positive type, it can be easily accomplished by adding a photoacid generator or a photoamine generator for the purpose of decomposing an acid labile group. As a result, semiconductors, substrates, optical devices,
It can be used in fields such as micromachines and electronic devices.

According to the present invention, at least one carboxylic acid of the dicarboxylic acid of the general formula (1) is substituted with a branched or cyclic alkyl group such as t-butyl group or tert-butoxycarbonyl via a spacer. Group, or an acid labile group such as a tBOC compound such as a tert-butoxycarbonylmethyl group can be used as a solubility control material in a positive photoresist. As the acid labile group in this case, all those used in a general chemically amplified photoresist can be applied.

Since the compound containing an acid labile group of the present invention does not use aromatic compounds and has a high fluorine content, not only g line and i line but also 248 nm, 193 n
It has excellent transparency even in a wavelength range of m, 157 nm or less, and can be mixed with a photoresist resin to form a high-performance chemically amplified positive photoresist composition. Further, a fluororesin containing a compound having an acid-decomposable substituent added to the dicarboxylic acid of the general formula (1) or one of the carboxylic acids of the present invention in the side chain is synthesized, and the resin is used in the above various wavelength bands. It can also be used as a photoresist resin.

[0057]

EXAMPLES The present invention will be described below with reference to examples.
The invention is not limited by these examples.

[Example 1] 200 g of 2,2-bis (4-carboxyphenyl) -hexafluoropropane was used as a raw material and charged into a 1 L autoclave together with 500 ml of hexafluoroisopropyl alcohol, and then Pt-C was added.
Was added as a catalyst.

After the inside of the reactor was replaced with hydrogen while stirring was stopped, the bath temperature was gradually raised and the reduction reaction was carried out at a hydrogen pressure of 1.0 MPa while adjusting the internal temperature to about 100 ° C. Since the absorption of hydrogen was almost completed in 2 hours, the reactor was cooled with ice and the hydrogen in the reactor was gradually purged. The reaction solution was filtered to remove Pt-C as the catalyst, and the product was isolated by distillation to obtain about 30 g of the product. The IR spectrum of the obtained compound is shown in FIG. This allows
It was found to be 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane of the general formula (1).

[Example 2] Bisphenol AF [2, 2]
-Bis (4-hydroxyphenyl) -hexafluoropropane] 6.7 g (0.02 mol), pyridine 3.5
g, and 37 g of dimethylacetamide were charged into a glass-lined autoclave equipped with a stirrer and uniformly mixed, and then the diacid of 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane obtained in Example 1 was obtained. 8.5 g (0.02 mol) of chloride was added portionwise over 20 minutes. During that time, the internal temperature was controlled to be 10 ° C. Then, the polymerization was allowed to proceed at room temperature for 5 hours, and then the reaction solution was added dropwise to excess methanol to precipitate the polymer. The precipitated polymer was separated by filtration and washed with methanol repeatedly, and then dried at 50 ° C. to obtain 12 g of fluorine-containing polyester. 0.1g / in dimethylacetamide
Dissolve at a concentration of dl, 30 ℃ by Ostwald viscometer
The reduced viscosity was 0.50 dl / g. When the obtained polymer was dissolved in dimethylacetamide and spread on a glass plate to form a film, it was a tough film having high transparency.

Example 3 A glass-lined autoclave equipped with a stirrer was charged with 2,2-bis (3-amino-).
4-hydroxyphenyl) hexafluoropropane 7.
00 g (0.02 mol), pyridine 3.5 g, and dimethylacetamide 37 g were charged, and the internal temperature was cooled to 1 ° C. with stirring. 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane dissolved therein, 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane diacid chloride 8 obtained in Example 1 0.5 g (0.02 mol) was added little by little over 20 minutes, reacted for 30 minutes to stop cooling, and after the addition, polymerization was allowed to proceed for 5 hours. Then, the reaction solution was dropped into excess methanol to precipitate the polymer. The precipitated polymer was separated by filtration and washed with methanol repeatedly, and then dried at 50 ° C. to obtain a fluorine-containing polyhydroxyamide. It was dissolved in dimethylacetamide at a concentration of 0.1 g / dl, and the reduced viscosity measured by an Ostwald viscometer at 30 ° C. was 0.70.
It was dl / g. The obtained fluorinated polyhydroxyamide is

[0062]

[Chemical 19]

It was a polymer comprising the structural unit of.

Next, the obtained fluorine-containing polyhydroxyamide was redissolved in dimethylacetamide to a concentration of 20% by weight, and a film having a thickness of 3 was formed on a glass plate by a solvent casting method.
A uniform film of 5 microns was obtained. Then 150 ℃,
It was dehydrated and condensed by heating at 230 ° C. and 300 ° C. for 30 minutes in sequence to obtain highly transparent fluorine-containing polybenzoxazole. The obtained fluorine-containing polybenzoxazole is

[0065]

[Chemical 20]

It is a polymer comprising the structural unit of.

The dielectric constant of the obtained fluorine-containing polybenzoxazole was measured and found to be 2.2 at 1 MHz.
It was 5. The linear thermal expansion coefficient of this film was measured and found to be 2 × 10 ⁻⁵ / ° C. as an average value of 50 to 300 ° C.
Met.

Example 4 In the same manner as in Example 1, a glass-lined autoclave equipped with a stirrer was used.
3'-Dihydroxy-4,4'-diaminobiphenyl 4.32 g (0.02 mol), pyridine 3.5 g, and dimethylacetamide 30 g were charged, and the internal temperature was 1 while stirring.
Cooled to ° C. When 2,3'-dihydroxy-4,4'-diaminobiphenyl was dissolved, 2,2-bis- (4-carboxycyclohexyl) -obtained in Example 1 was obtained.
Hexafluoropropane diacid chloride 8.5g
(0.02 mol) in small portions over 20 minutes, 30
The reaction was carried out for 1 minute, the cooling was stopped, and the polymerization was allowed to proceed for 5 hours after the addition. Then, the reaction solution was dropped into excess methanol,
The polymer was precipitated. The precipitated polymer was separated by filtration and washed with methanol repeatedly, and then dried at 50 ° C. to obtain a fluorine-containing polyhydroxyamide. It was dissolved in dimethylacetamide at a concentration of 0.1 g / dl, and the reduced viscosity measured by an Ostwald viscometer at 30 ° C. was 0.75 dl / g. The obtained fluorinated polyhydroxyamide is

[0069]

[Chemical 21]

It was a polymer comprising the structural unit of.

The resulting fluorine-containing polyhydroxyamide was redissolved in dimethylacetamide to a concentration of 20% by weight, and solvent casting was performed to obtain a uniform film having a thickness of 34 μm on a glass plate. Then 150 ° C, 230
The mixture was dehydrated and condensed by sequentially heating at 30 ° C. and 300 ° C. for 30 minutes to obtain fluorine-containing polybenzoxazole. The obtained fluorine-containing polybenzoxazole is

[0072]

[Chemical formula 22]

It was a polymer composed of the structural unit of.

The dielectric constant of the obtained fluorine-containing polybenzoxazole was measured and found to be 2.5 at 1 MHz.
Met. The linear thermal expansion coefficient of this film was measured and found to be an average value of 50 to 300 ° C. of 1.8 × 10 ⁻⁵ /
It was ℃.

Example 5 20 g of t-butanol, 3.5 g of pyridine, and 37 g of dimethylacetamide were placed in a glass-lined autoclave equipped with a stirrer and uniformly mixed, and then 2,2 obtained in Example 1 was used. -Bis- (4-carboxycyclohexyl) -hexafluoropropane diacid chloride 8.5 g (0.02 mol)
Was added in small portions over 20 minutes. Then, at room temperature, 5
The esterification reaction was allowed to proceed for a period of time. After completion of the reaction, 2,2-bis- (4-carboxycyclohexyl) was obtained by distillation.
The di-t-butylated product of hexafluoropropane
3 g was obtained. This compound was insoluble in 2.38% tetramethylammonium hydroxide, which is a photoresist developing solution.

Next, the di-t of the name 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane
-Butylated product was dissolved in butyl acetate to a concentration of 10% and triphenylsulfonium trifluoromethanesulfonate at a concentration of 0.1%, and irradiated with a 248 nm KrF laser. After that, when the solvent was evaporated,
The developer was 2.38% tetramethylammonium hydroxide. Therefore, it was found that this compound can be used as an additive for photoresists.

[0077]

The fluorine-containing polybenzoxazole of the present invention exhibits a low dielectric constant and a low coefficient of thermal expansion while maintaining the properties such as mechanical strength and thermal stability, and therefore, it can be used as an insulating material for optical and electronic parts or as an optical material. It is useful as a coating material for parts.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of 2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane.

Continued front page    F-term (reference) 2H025 AB16 AB17 AC08 BE07 CC20                 4H006 AA01 AB46 AB84 BJ20 BM10                       BM71 BS20                 4J031 BA06 BA07 BA09 BA11 BB01                       BB02 BB03 BD13 BD22                 4J043 PA01 PC145 PC146 QB15                       QB16 QB28 QB33 QB47 QB58                       QB68 RA04 RA05 RA23 RA24                       RA52 SA06 SA11 SA54 SA71                       SA78 SA85 TA11 TA12 TA47                       TA70 TB01 UA042 UA122                       UA132 UA142 UA152 UB012                       UB062 UB122 UB152 UB292                       UB302 UB402 ZB03 ZB22

Claims (7)

[Claims] 1. A fluorinated dicarboxylic acid represented by the formula (1). [Chemical 1] 2. A fluorine-containing polymer obtained by polymerizing the fluorine-containing dicarboxylic acid represented by the formula (1) according to claim 1 or an amide-forming compound or ester-forming derivative thereof. 3. A general formula (2): (In the formula, X is a tetravalent organic group containing an aromatic ring, and two sets of N and O are ortho to each other in the aromatic ring of X so as to form a five-membered ring.). A fluorine-containing polybenzoxazole containing a structural unit represented. 4. X is represented by the general formula (3): (In the formula, each aromatic ring has a dangling bond at the ortho position,
The hydrogen atom of the aromatic ring may be substituted with halogen (fluorine, chlorine, bromine and iodine). 4. The fluorinated polybenzoxazole according to claim 3, which is an organic group represented by 5. A compound represented by the general formula (4): (In the formula, X is the same as X in the general formula (2) described in claim 2) A fluorine-containing polyhydroxyamide. 6. A coating composition in which the polymer according to any one of claims 2 to 4 is dissolved in an organic solvent. 7. A composition for a photosensitive material, wherein at least one carboxylic acid of the dicarboxylic acid of the general formula (1) according to claim 1 is modified with an acid labile group.