JP2003183387A - Fluorine-containing alicylic diamine and polymer using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer obtained from a novel fluorine-containing alicyclic diamine, which is useful as an insulating material of electronic parts having a low dielectric constant, heat resistance, and sufficient toughness at the same time or an optical part, and the polymer such as a polyamide, a polyamic acid, and a polyimide which uses the same. <P>SOLUTION: The fluorine-containing alicyclic diamine contains at least two cyclohexyl rings and two fluoroalkyl groups in the molecule, and the fluoride- containing alicyclic polymer compound uses the same are provided. The fluorine- containing alicyclic polyamide and the fluorine-containing polyamic acid use a compound of formula (1) or formula (2) at least as part of the monomers, and furthermore the fluorine-containing polyimide is obtained by cyclizing the fluorine-containing polyamic acid. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluorine-containing alicyclic diamine useful as an electrical insulator or an optical component having a low dielectric constant and high transparency, and a polyamide using the same.
It relates to polymers such as polyimide.

[0002]

2. Description of the Related Art Generally, a diamine having an aromatic structure is used as a raw material monomer for polyamide, polyimide or a precursor thereof, polyamic acid.

In particular, polyimide is easily obtained by reacting an aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride with an aromatic diamine such as diaminodiphenyl ether in an equimolar reaction in an aprotic polar solvent such as dimethylacetamide. It is flexible because it is obtained by molding a polyimide precursor with a high degree of polymerization into a film and curing it by heating, and has excellent heat resistance, chemical resistance, radiation resistance, electrical insulation, mechanical properties, etc. It is currently widely used for various electronic devices such as printed wiring circuit boards, tape automation bonding substrates, protective films for semiconductor elements, and interlayer insulating films for integrated circuits.

Recently, in particular, an increase in the operating speed of a microprocessor and a reduction in the rise time of a clock signal have become important issues in the information processing and communication fields. For that purpose, a polyimide film used as an insulating film is required. It is necessary to lower the dielectric constant of.

In order to reduce the dielectric constant of polyimide, it is necessary to introduce a fluorine group into the polyimide structure (Macrom
olecules, 24, 5001 (199
1)) or a method of interfering with intramolecular conjugation and charge transfer complex formation by replacing aromatic units with alicyclic units to reduce d electrons (Macromolecules,
32, 4933 (1999)).
That is, for example, a polyimide synthesized from pyromellitic dianhydride and a fluorine-containing aromatic diamine such as 2,2′-bis (trifluoromethyl) benzidine, which is a rigid fluorine group-containing diamine, can achieve low thermal expansion characteristics. However, the dielectric constant is not so low (Macro
molecules, 26, 419 (199
3)). In addition, polyimides that have been converted from aromatics to alicyclics have not yet been reported to have sufficiently low dielectric constants.

On the other hand, introduction of an aliphatic group into polyimide is also effective for lowering the dielectric constant. However, in reality, the synthesis of a fluorine-containing alicyclic diamine in which fluorine and an alicyclic group are included in the same monomer unit has been relatively difficult, and thus it has not been realized so far. .

[0007]

DISCLOSURE OF THE INVENTION The present invention uses a novel fluorine-containing alicyclic diamine which has a low dielectric constant, heat resistance, and sufficient toughness and is useful as an insulating material for electronic parts or an optical part. It provides a polymer such as polyamide, polyamic acid, or polyimide.

[0008]

In view of the above problems, as a result of intensive studies, a fluorine-containing alicyclic ring having a specific structure containing at least two cyclohexyl rings and two fluoroalkyl groups in a molecule as a diamine. The present invention has been completed by discovering the formula diamine and further discovering the fluorine-containing alicyclic polymer using this as the polymerizable monomer.

That is, the present invention is a fluorinated alicyclic diamine containing at least two cyclohexyl rings and two fluoroalkyl groups in the molecule. Suitably, the diamine shown by Formula (1) or Formula (2) can be illustrated.

[0010]

[Chemical 9]

[0011]

[Chemical 10]

The present invention also relates to a fluorine-containing polymer compound in which a fluorine-containing alicyclic diamine containing at least two cyclohexane rings and two fluoroalkyl groups in the molecule is used as at least a part of the monomer. is there. Preferably, the above-mentioned formula (1) or formula (2) is used as at least a part of the monomer, a fluorinated alicyclic polyamide, a fluorinated polyamic acid, and further a fluorinated polyamic acid cyclized. Fluorine polyimide.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.

The present invention provides a fluorine-containing alicyclic diamine having a specific structure containing at least two cyclohexane rings and two fluoroalkyl groups in the molecule, and a polyamide obtained by reacting the diamine with a dicarboxylic acid or a derivative thereof. The present invention relates to a polyamic acid for reacting the diamine and a tetracarboxylic dianhydride component and a polyimide obtained by cyclizing the polyamic acid.

The structure of the fluorinated alicyclic diamine of the present invention is not particularly limited as long as it contains at least two cyclohexane rings and two fluoroalkyl groups in the molecule, but the following formula (1), The fluorine-containing diamine represented by (2) is preferably adopted.

[0016]

[Chemical 11]

[0017]

[Chemical 12]

The synthesis method and production method of the diamine containing at least two cyclohexane rings and two fluoroalkyl groups in the molecule of the present invention are not particularly limited.
As an example, at least two benzene rings and two in the molecule
A method for obtaining a diamine containing one fluoroalkyl group by a reduction reaction with hydrogen can be proposed. However, it is generally considered difficult to reduce the aromatic ring of the fluorine-containing aromatic diamine, and it has not been realized so far. Therefore, as a result of diligent examination of the reaction conditions, the present inventors succeeded in advancing the reduction reaction by optimizing the conditions such as solvent, catalyst, temperature and pressure.

In the present invention, it is necessary to use a fluorine-containing diamine containing two cyclohexane rings and two fluoroalkyl groups in the molecule of formula (1), formula (2), etc., but other general reports have been made. Any diamine may be used together without any particular limitation. Specific examples of preferred diamines that can be used in combination include 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, and 3,3′-bistrifluoromethyl-4,4 ′.
-Diaminobiphenyl, 3,3'-bistrifluoromethyl-5,5'-diaminobiphenyl, bis (trifluoromethyl) -4,4'-diaminodiphenyl, bis (fluorinated alkyl) -4,4'-diaminodiphenyl , Dichloro-4,4'-diaminodiphenyl, dibromo-4,4'-diaminodiphenyl, bis (fluorinated alkoxy) -4,4'-diaminodiphenyl, diphenyl-4,4'-diaminodiphenyl, 4,4 ' -Bis (4-aminotetrafluorophenoxy) tetrafluorobenzene, 4,4'-bis (4-aminotetrafluorophenoxy) octafluorobiphenyl, 4,4'-
Binaphthylamine, o-, m-, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminodurene, dimethyl-4,4'- Diaminodiphenyl, dialkyl-4,4'-diaminodiphenyl, dimethoxy-4,4'-diaminodiphenyl, diethoxy-4,
4'-diaminodiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,3-bis (3- Aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (3-aminophenoxy) phenyl) sulfone, bis (4 -(4-aminophenoxy) phenyl) sulfone, 2,2-bis (4- (4-aminophenoxy) phenyl) propane,
2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3
-Aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-amino-2)
-Trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (3-amino-5)
-Trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl)
Hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3-
Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 4,4′-bis (4-aminophenoxy) octafluorobiphenyl, 4,4 ′
-Diaminobenzanilide and the like can be exemplified. Two or more of these may be used in combination.

Further, in the present invention, a diamine having a hydroxyl group in the molecule can also be used as a monomer that can be used in combination. Specific examples of bis (aminophenol) compounds include 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. In addition, the above-mentioned bis (aminophenol)
A trialkylsilyl compound of a bis (aminophenol) compound in which a trialkylsilyl group is added to the compound can also be used for the purpose of increasing the polymerization reactivity. These bis (aminophenol) compounds are 3,3'-bis (trimethylsiloxy) -4,4'-bis (as shown in Macromolecules, Vol. 21, page 2305 (1988) and below. It can be adjusted according to the method for producing trimethylsilylamino) biphenyl. For example, 3,3′-bis (trialkylsiloxy) -4,4 is obtained by reacting trialkylsilyl chloride in a tetrahydrofuran solution of 4,4′-diamino-3,3′-dihydroxybiphenyl in the presence of triethylamine. ′ -Bis (trialkylsilylamino) biphenyl can be obtained.

The polymers obtained in the present invention are all polymers using the above-mentioned fluorine-containing diamine as a constitutional unit, and the structure thereof is not limited. That is, a monomer having a functional group capable of reacting with an amine of the above-mentioned diamine compound can be used as a partner component for polymerization, and the type of polymer produced varies depending on the type of the partner. For example, when a dicarboxylic acid compound is selected, a fluorinated alicyclic polyamide can be produced. When an acid anhydride of tetracarboxylic acid is selected, a fluorinated alicyclic polyamic acid and polyimide can be produced. Furthermore, by combining the other components, a polymer containing an amide bond, an imide bond, or a urea bond such as polyamideimide, polyetheramide, polyetherimide, polyesteramide, polyesterimide, or polyurea can be produced. The primary structure of the polymer may be a linear structure or a branched structure in the molecule and may be used without limitation. Furthermore, highly branched polymers, for example, structures called dendrimers and hyperbranches can also be adopted.

As examples of the polymer that can be used in the present invention, production examples of polyamide, polyamic acid and polyimide will be described.

As a method for producing polyamide, a known method can be used without particular limitation. That is, if one example is shown, with respect to the above-mentioned diamine, dicarboxylic acid, or dichloride of dicarboxylic acid which is an acid component containing an amide-forming derivative thereof, an acid halide such as dibromide,
For example, the polymer represented by the general formula (3) or (4) can be produced by reacting a dialkyl ester such as dimethyl ester or diethyl ester of the dicarboxylic acid. In this case, it is also possible to use a polymer dissolution accelerator which is often added to the polymerization of polyamide, that is, a metal salt such as lithium bromide or lithium chloride, or a dehydrating agent such as sulfuric acid. That is, a fluorinated alicyclic polyamide containing the repeating unit of the general formula (3) is produced.

[0024]

[Chemical 13]

[0025]

[Chemical 14]

(In the formula, R is a straight chain, branched chain, alicyclic ring, aromatic ring,
It is one or more divalent groups selected from heterocycles and may partially contain fluorine, oxygen, or nitrogen).

The dicarboxylic acid compounds usable in the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Aliphatic dicarboxylic acids such as 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'-dicarboxyldiphenylmethane, 4,4'-dicarboxyldiphenylmethane, 3,3'-dicarboxyldiphenyldifluoromethane, 3,4'-dicarboxyldiphenyldifluoromethane, 4,4'-dicarboxyldiphenyldifluoromethane, 3 , 3'-dicarboxyl diphenyl sulfone, 3,4'-dicarboxyl diphenyl sulfone, 4,4'-dicarboxyl diphenyl 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 (3,3
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, 2,2'-bis (trifluoromethyl) -4,4 ' -Biphenyldicarboxylic acid, 1,3-bis (3-carboxyphenoxy) benzene, 1,4-bis (3-carboxyphenoxy) benzene, 1,4-bis (4-carboxyphenoxy) benzene, 3,3 '-( 1,4-Phenylenebis (1-methylethylidene)) bisbenzoic acid, 3,4 ′-(1,4-
Phenylene bis (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-carboxy) Phenoxy) 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) terephthalic acid, 4-
Dicarboxylic acids containing a perfluorononenyloxy group such as methoxy-5- (perfluorononenyloxy) isophthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) phthalic acid, 2- Aromatic dicarboxylic acids such as perfluorohexenyloxy group-containing dicarboxylic acids such as (perfluorohexenyloxy) terephthalic acid and 4-methoxy-5- (perfluorohexenyloxy) isophthalic acid can be exemplified. Further, an alicyclic dicarboxylic acid obtained by reducing the aromatic ring of the above-mentioned dicarboxylic acid with hydrogen can also be used.

Next, the polyamic acid according to the present invention will be described. As a method for producing a polyamic acid, a known method can be used without particular limitation, and the method of mixing a diamine and an acid dianhydride in a solvent and performing a polycondensation reaction is the simplest. The ratio of the total number of moles of the diamine mixture used for the polymerization to the total number of moles of the tetracarboxylic dianhydride is 0.5 to 1.5.
Is generally in the range of 0.8 to 1.2
It is preferably in the range of. As with the usual polycondensation reaction, the closer this ratio is to 1, the higher the molecular weight of the polymer obtained.

By reacting the above diamine with a tetracarboxylic acid anhydride, a fluorine-containing alicyclic polyamic acid represented by the general formulas (5) and (6) or an ester thereof can be produced (wherein R ₁ Is a straight chain, branched, alicyclic, aromatic ring,
One or more tetravalent groups selected from heterocycles, which may partially contain fluorine, oxygen, or nitrogen, R ₂ is hydrogen, a straight-chain or branched alkyl group having 1 to 20 carbon atoms. And may partially contain fluorine, oxygen, nitrogen, an unsaturated bond, or a cyclic structure).

[0030]

[Chemical 15]

[0031]

[Chemical 16]

A method of reacting a disilylated aliphatic diamine with an acid dianhydride to synthesize a silyl ester of a polyamic acid (Proceedings of the Symposium on Polymers, 49, 1917)
(2000)) or the like can be adopted.

The structure of the tetracarboxylic dianhydride that can be used in the present invention is not particularly limited, and examples thereof include benzenetetracarboxylic dianhydride (pyromellitic dianhydride; PMDA) and trifluoromethylbenzenetetraanhydride. Carboxylic dianhydride, bistrifluoromethylbenzenetetracarboxylic dianhydride, difluorobenzenetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, terphenyltetracarboxylic dianhydride,
Hexafluoroisopropylidene diphthalic acid dianhydride,
Oxydiphthalic acid dianhydride, bicyclo (2,2,2) oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) phene Xafluoropropanoic acid dianhydride (6FDA)
And so on.

A solvent can be used in the polymerization reaction of the polyamic acid of the present invention. Examples of such a solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N
Examples thereof include aprotic solvents such as -methyl-2-pyrrolidone, hexamethylphosphoramide, and dimethyl sulfoxide, but the structure thereof is not particularly limited as long as the diamine as the raw material monomer and the partner component are dissolved. That is,
Specific examples include N-methylpyrrolidone, sulfolane, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, γ-butyrolactone, γ-valerolactone, a-valerolactone, γ-caprolactone. , A-caprolactone, α-methyl-γ-
Butyrolactone, ethylene carbonate, propylene carbonate, triethylene glycol, acetophenone, 1,3-dimethyl-2-imidazolidinone, N, N
-Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like are preferably adopted.
These may be used alone or in combination.

In addition, other common organic solvents, such as phenol, o-cresol, butyl acetate, ethyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate,
Butyl cellosolve acetate, ethyl acetate, butyl acetate, 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 type solvents, etc. can also be added and used.

The polymer of the present invention obtained as described above is applied as a shape or a product such as a varnish dissolved in an organic solvent, a film or a molded product obtained by removing the solvent, or a molded product obtained from a powder. Will be donated.

At that time, if necessary, additives such as an oxidation stabilizer, a filler, a silane coupling agent, a photosensitizer, a photopolymerization initiator and a sensitizer may be mixed in the obtained polymer. It doesn't matter.

The above-described polyamic acid of the present invention can be converted into a fluorine-containing alicyclic polyimide by subjecting it to an imidization reaction with heating or a dehydrating reagent. When the heat imidization is performed, the treatment can be performed at a temperature of 80 to 400 ° C., but a temperature range of 150 to 350 ° C. is particularly preferable. When the imidization temperature is 150 ° C. or lower, the imidization ratio is low and the film strength of the polyimide film is impaired.
If the temperature is higher than 0 ° C, the coating film becomes colored or becomes brittle, which is a problem. Further, instead of heat treatment, it may be chemically performed by reacting with a dehydrating reagent such as acetic anhydride.

The polyimide obtained in the present invention has the following general formulas (7) and (8) obtained by subjecting the polyamic acid of the general formula (5) or (6) to an imidization reaction with heating or a dehydrating reagent. It is a polymer containing the structural unit shown in the molecule (wherein R ₁ is one or more tetravalent groups selected from straight chain, branched chain, alicyclic ring, aromatic ring and hetero ring,
It may partially contain fluorine, oxygen and nitrogen).

[0040]

[Chemical 17]

[0041]

[Chemical 18]

The thus obtained polyimide compound of the present invention has a low dielectric constant, heat resistance, and sufficient toughness, so that it can be applied to the field of electronic material devices, such as substrates for flexible printed wiring circuits and tape automation bonding. It is useful as an insulating film for electronic parts or an optical part, such as a substrate for semiconductors, a protective film for semiconductor elements, an interlayer insulating film for integrated circuits, and the like.

[0043]

The present invention will be described in detail below with reference to examples, but the invention is not necessarily limited to these.

Example 1 Synthesis of 2,2-bis (4-aminocyclohexyl) -hexafluoropropane (diamine (1); formula (1))

In a 1 liter autoclave equipped with a stirrer, 2,2-bis (4-aminophenyl)-
Hexafluoropropane 100g (0.30 mo
l), hexafluoroisopropyl alcohol 500
g, 17 g of 2.5% Pt-2.5% Pd / C supported catalyst was added.

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 the catalyst (2.5% Pt-2.5% Pd / C), and the product was isolated by distillation to give about 2
9 g of diamine (1) was obtained (yield 28.3%).
The NMR data of the obtained compound are shown below. ¹ H-NMR data (dimethyl sulfoxide d ₆ ; pp
m) 1.00-1.08 (m, 1H), 1.28-
1.37 (m, 1H), 1.44-1.63 (m, 1.
2H), 1.77-1.96 (m, 3.5H), 2.0
9 (br, 1.2H), 3.11 (br, 0.17H)

"Example 2" Synthesis of 2,2'-bis (trifluoromethyl) -4,4'-diaminobicyclohexyl (diamine (2); formula (2))

In a 1-liter autoclave equipped with a stirrer, 2,2'-bis (trifluoromethyl) was added.
Benzidine 100 g (0.31 mol), hexafluoroisopropyl alcohol 500 g, (2.5% Pt-
17 g of 2.5% Pd / C) supported catalyst was added.

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 the catalyst (2.5% Pt-2.5% Pd / C), and the product was isolated by distillation to give about 2
2 g of diamine (2) was obtained (yield 21.6%).
The NMR data of the obtained compound are shown below. ¹ H-NMR data (dimethyl sulfoxide d ₆ ; pp
m) 0.76-1.27 (m, 1.7H), 1.47
-1.87 (m, 2.4H), 2.03-2.06
(M, 0.5H), 2.62-2.90 (m, 1H)

[Examples 3 and 4] The diamines (1) and (2) synthesized in Examples 1 and 2 and the dicarboxylic acid (2,2-bis- (4-carboxycyclohexyl) -hexafluoropropane shown in the figure below. : Formula (9); hereinafter, H
-BIS-B-AF) was reacted to synthesize a polyamide.

[0051]

[Chemical 19]

Example 3 Synthesis of Polyamide (Diamine (1) / H-Bis-B-AF) System The diamine synthesized in Example 1 was placed in a 300-ml three-necked flask equipped with a stirrer and a cooling tube. 1) 1.00 g
(2.89 mmol), H-Bis-B-AF (2,
2-bis- (4-carboxycyclohexyl) -hexafluoropropane) 1.17 g (2.89 mmo)
l), triphenyl phosphite 1.79 g (5.78 mm)
ol), 1.5 ml of pyridine, and 15 ml of N-methyl-2-pyrrolidone were added, and the mixture was stirred at 100 ° C. for 3 hours under a nitrogen stream. The resulting reaction solution was allowed to cool to room temperature and then poured into methanol / water (1/1 vol%) to precipitate a polymer. After filtration and recovery, the product was dried under reduced pressure at 100 ° C. to obtain 1.75 g of a powdery fluorine-containing alicyclic polyamide (formula (20)) (yield 85%).

[0053]

[Chemical 20]

When this polyamide was dissolved in dimethylacetamide and treated at 200 ° C. for 1 hour and 300 ° C. for 1 hour, a transparent film was obtained.

Example 4 Synthesis of Polyamide (Diamine (2) / H-Bis-B-AF) System The diamine (synthesized in Example 2 was placed in a 300-ml three-necked flask equipped with a stirrer and a cooling tube. 2) 1.00g
(3.01 mmol), H-Bis-B-AF1.2
2 g (3.01 mmol), triphenyl phosphite 1.87 g (6.02 mmol), pyridine 1.5 m
1, 15 ml of N-methyl-2-pyrrolidone were added, and the mixture was stirred at 100 ° C. for 3 hours under a nitrogen stream. The same treatment as in Example 3 was performed to obtain 1.89 g of a powdery fluorine-containing alicyclic polyamide (formula (11)) (yield 90%).

[0056]

[Chemical 21]

When this polyamide was dissolved in dimethylacetamide and treated at 200 ° C. for 1 hour and 300 ° C. for 1 hour, a transparent film was obtained.

"Examples 5 to 8" Diamine (1)
Alternatively, by using (2), 4,4 ′-(hexafluoroisopropylidene) diphthalic acid dianhydride (hereinafter, referred to as 6FDA) or pyromellitic dianhydride (hereinafter, PMDA)
, And polyamic acid was synthesized.

Example 5 Polyamic acid (formula (1
2)) Synthesis (Diamine (1) / 6FDA) 1.12 g (3.25 m) of the diamine (1) synthesized in Example 1 in a 300-ml three-necked flask equipped with a stirrer.
mol), 6FDA 1.44 g (3.25 mmo)
1) and 12.5 ml of N-methyl-2-pyrrolidone were added, and the mixture was stirred at 80 ° C. for 3 hours under a nitrogen stream. The reaction solution obtained was allowed to cool to room temperature and then methanol / water (1/1 v
ol%) to precipitate the polymer. After filtration and recovery, the product was dried under reduced pressure at 40 ° C. to obtain 2.54 g of a white powder of fluorine-containing alicyclic polyamic acid (formula (12)) (yield 99.
%). The IR spectrum of the obtained polyamic acid is shown in FIG.

[0060]

[Chemical formula 22]

Example 6 Polyamic acid (formula (1
Synthesis of (3)) (diamine (2) / 6FDA) 1.30 g of the diamine (2) synthesized in Example 2 (3.54 m) in a 300-ml three-necked flask equipped with a stirrer.
mol), 6FDA 1.57 g (3.54 mmo
1) and 13.4 ml of N-methyl-2-pyrrolidone were added, and the mixture was stirred at 80 ° C. for 3 hours under a nitrogen stream. The same treatment as in Example 5 was carried out to obtain 2.67 g of a white powdery fluorine-containing alicyclic polyamic acid (formula (13)) (yield: 9
7%). The IR spectrum of the obtained polyamic acid is shown in FIG.
It was shown to.

[0062]

[Chemical formula 23]

Example 7 Synthesis of Polyamic Acid (Diamine (1) / PMDA) 1.12 g (3.25 g) of diamine (1) synthesized in Example 1 was placed in a 300-ml three-necked flask equipped with a stirrer.
mmol), 0.71 g of pyromellitic dianhydride (32
5 mmol), N-methyl-2-pyrrolidone 12.5
ml was added and the mixture was stirred at 80 ° C. for 3 hours under a nitrogen stream. The same treatment as in Example 5 was performed to obtain 1.65 g of a white powdery fluorinated alicyclic polyamic acid (yield 90%).

[0064]

[Chemical formula 24]

Example 8 Synthesis of Polyamic Acid (Diamine (2) / PMDA) 1.18 g of diamine (2) synthesized in Example 2 in a 300-ml three-necked flask equipped with a stirrer (3. 54
mmol), 0.77 g of PMDA (3.54 mmo)
1) and 13.4 ml of N-methyl-2-pyrrolidone were added, and the mixture was stirred at 80 ° C. for 3 hours under a nitrogen stream. The same treatment as in Example 5 was performed to obtain 1.82 g of a white powdery fluorinated alicyclic polyamic acid (formula (15)) (yield 93.
%).

[0066]

[Chemical 25]

[Examples 9 to 12] Polyimides were synthesized from the polyamic acids obtained in Examples 5 to 8.

Example 9 Polyimide (formula (16))
Of the polyamic acid (Formula (12)) 0.5 obtained in Example 5
4 g was weighed and dissolved in dimethylacetamide. Then, after spreading on a clean glass plate, under a nitrogen stream, 20
When heat-treated at 0 ° C. for 1 hour and at 300 ° C. for 1 hour, a transparent fluorine-containing alicyclic polyimide film 0.4
7 g was obtained (yield 92%). The IR spectrum of the obtained polyimide film is shown in FIG.

[0069]

[Chemical formula 26]

Further, as a result of thermal analysis of the obtained polyimide film, the temperature at which 5% weight decreased (thermal decomposition temperature) was 505 ° C. Further, it was revealed that the light transmittance at a wavelength of 650 nm of visible light was as high as 94% for a 150-micron film, and the dielectric constant at 1 MHz was 2.51, which was a low dielectric film.

Example 10 Polyimide (formula (1
7)) Synthesis of polyamic acid obtained in Example 6 (formula (13))
When 51 g was weighed and formed into a film and heat-treated in the same manner as in Example 9 to produce a polyimide film,
Transparent fluorine-containing alicyclic polyimide film 0.45g
(Formula (17)) was obtained (yield 93%). The IR spectrum of the obtained film is shown in FIG.

[0072]

[Chemical 27]

It was found to be a polymer composed of the structural unit of.

Furthermore, as a result of thermal analysis of the obtained polyimide film, the temperature at which 5% weight loss (thermal decomposition temperature) was 510 ° C. Further, it was revealed that the light transmittance at a wavelength of 650 nm of visible light was as high as 95% for a 150-micron film and showed a low dielectric constant of 2.45 at 1 MHz.

Example 11 Polyimide (formula (1
8)) Synthesis of polyamic acid obtained in Example 7 (formula (14)) 0.6
When 1 g was weighed and formed into a film and heat-treated in the same manner as in Example 9 to produce a polyimide film, a transparent fluorine-containing alicyclic polyimide film (formula (18)) was obtained.
0.53 g was obtained (yield 92%).

[0076]

[Chemical 28]

Further, as a result of thermal analysis of the obtained polyimide film, the temperature at which 5% weight loss (thermal decomposition temperature) was 520 ° C. Further, it was revealed that the light transmittance at a wavelength of 650 nm of visible light was as high as 88% for a 150-micron film, and the dielectric constant at 1 MHz was 2.7, which was a low dielectric film.

Example 12 Polyimide (formula (1
9)) Synthesis of polyamic acid obtained in Example 8 (formula (15)) 0.5
When 0 g was weighed and formed into a film and heat-treated in the same manner as in Example 9 to produce a polyimide film, a transparent fluorine-containing alicyclic polyimide film (formula (19)) was obtained.
0.43 g was obtained (yield 92%).

[0079]

[Chemical 29]

Further, as a result of thermal analysis of the obtained polyimide film, the temperature at which 5% weight loss (thermal decomposition temperature) was 525 ° C. Further, it was revealed that the light transmittance at a wavelength of 650 nm of visible light was as high as 91% for a 150-micron film, and the dielectric constant at 1 MHz was 2.6, which was a low dielectric film.

[Brief description of drawings]

FIG. 1 shows IR spectra of a polyamic acid of Example 5 (formula (12)) and a polyamic acid of Example 6 (formula (13)).

FIG. 2 shows IR spectra of the polyimide of Example 9 (formula (16)) and the polyimide of Example 10 (formula (17)).

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuhiko Maeda             3-7-1 cent Kandanishikicho, Chiyoda-ku, Tokyo             Inside Ral Glass Co., Ltd. F-term (reference) 4H006 AA01 AA03 AB46                 4J001 DA01 DC14 EB03 EB05 EB06                       EB07 EB08 EB09 EB35 EB36                       EB37 EB55 EB56 EB57 EB58                       EB60 EB64 EC36 EC54 EC66                       GA13 JA07 JB37 JB42                 4J043 PA02 QB15 QB26 QB31 RA05                       RA34 SA06 SA54 SB01 TA71                       TB01 UA131 UA132 UB021                       UB022 UB051 UB122 UB302                       VA041 XA16 XB17 XB26                       ZA42 ZA46 ZA52 ZB47 ZB50

Claims (10)

[Claims] 1. A fluorinated alicyclic diamine containing at least two cyclohexyl rings and two fluoroalkyl groups in the molecule. 2. The fluorinated alicyclic diamine according to claim 1, which is represented by the formula (1). [Chemical 1] 3. The fluorinated alicyclic diamine according to claim 1, which is represented by the formula (2). [Chemical 2] 4. A fluorine-containing polymer compound in which a fluorine-containing alicyclic diamine containing at least two cyclohexyl rings and two fluoroalkyl groups in the molecule is used as at least a part of the monomer. 5. The fluorine-containing alicyclic polyamide structure containing a repeating unit of the general formula (3), wherein the fluorine-containing diamine according to claim 2 is used as at least a part of a monomer, and the fluorine-containing alicyclic polyamide structure according to claim 4. Fluorine-containing polymer compound. [Chemical 3] (In the formula, R is one or more divalent groups selected from a straight chain, a branched chain, an alicyclic ring, an aromatic ring and a hetero ring, and is partially fluorine,
May contain oxygen and nitrogen) 6. A fluorine-containing alicyclic polyamide structure having a fluorine-containing alicyclic polyamide structure containing a repeating unit of the general formula (4), wherein the diamine according to claim 3 is used as at least a part of a monomer. Polymer compounds. [Chemical 4] (In the formula, R is one or more divalent groups selected from a straight chain, a branched chain, an alicyclic ring, an aromatic ring and a hetero ring, and is partially fluorine,
May contain oxygen and nitrogen) 7. A fluorine-containing alicyclic polyamic acid of the general formula (5) or an ester thereof, wherein the diamine according to claim 2 is used as at least a part of the monomer. Molecular compound. [Chemical 5] (In the formula, R ₁ is one or more tetravalent groups selected from straight chain, branched chain, alicyclic ring, aromatic ring and heterocyclic ring, and may partially contain fluorine, oxygen and nitrogen. ₂ is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, which may partially contain fluorine, oxygen, nitrogen, an unsaturated bond, or a cyclic structure.) 8. A fluorine-containing high polycarboxylic acid according to claim 4, which is a fluorine-containing alicyclic polyamic acid of the general formula (6) or an ester thereof, wherein the diamine according to claim 3 is used as at least a part of the monomer. Molecular compound. [Chemical 6] (In the formula, R ₁ is one or more tetravalent groups selected from straight chain, branched chain, alicyclic ring, aromatic ring and heterocyclic ring, and may partially contain fluorine, oxygen and nitrogen. ₂ is hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, which may partially contain fluorine, oxygen, nitrogen, unsaturated bond, or cyclic structure) 9. The fluorine-containing alicyclic polyimide represented by the general formula (7), which is obtained by subjecting the polyamic acid according to claim 7 to an imidization reaction with heating or a dehydrating reagent. Polymer compounds. [Chemical 7] (In the formula, R ₁ is one or more tetravalent groups selected from straight chain, branched chain, alicyclic ring, aromatic ring, and hetero ring, and may partially contain fluorine, oxygen, or nitrogen.) 10. The fluorine-containing alicyclic polyimide represented by the general formula (8), which is obtained by subjecting the polyamic acid according to claim 8 to an imidization reaction with heating or a dehydrating reagent. Molecular compound (In the formula, R ₁ is one or more tetravalent groups selected from straight chain, branched chain, alicyclic ring, aromatic ring, and hetero ring, and may partially contain fluorine, oxygen, or nitrogen.)