JP4679357B2 - Fluorine-containing diamine and polymer using the same - Google Patents

Description

  The present invention relates to a novel hexafluoroisopropanol group-containing diamine or derivative thereof, and further to a polymer obtained using the hexafluoroisopropanol group-containing diamine or derivative thereof.

  In general, diamine is used as a monomer for condensation or addition polymerization such as polyimide, polyamide, polyamine, and polyurea. The obtained polymer mainly has a cyclic structure in the molecule, so that it has many mechanical strengths such as tensile strength and bending strength, and excellent thermal stability such as thermal decomposition temperature and thermal deformation temperature. Yes, it is positioned as a high-performance engineering plastic.

  These resins are used in various applications such as engineering plastics, heat-resistant coating materials, electronic materials, electronic component materials, and optical materials, but with the development of communication equipment, especially assuming applications to semiconductors and optical components. As needs for high-speed processing and high-frequency processing are increasing, low dielectric constant and high transparency are required as a result. In addition, low thermal expansion is an important point. As means for imparting such a low dielectric constant and means for imparting high transparency, fluorine-containing polymers that lower the electron density have been actively studied. For example, Non-Patent Document 1 has a description of lowering the dielectric constant of a fluorine-containing polyimide, and Non-Patent Document 2 cited therein has a lower dielectric constant by increasing the fluorine content. Is disclosed.

  Fluorine-containing compounds have features such as low water absorption, heat resistance, weather resistance, corrosion resistance, transparency, low refractive index, and low dielectric properties of fluorine atoms. And is mainly applied in the coating field at each wavelength.

Conventionally, as a method for increasing the fluorine content in the fluoropolymer, a method of introducing a long chain perfluoroalkyl or a method of substituting hydrogen of an aromatic ring with fluorine is known. Adhesiveness to the silicon substrate is reduced. For example, Patent Document 3 discloses an invention of an optical waveguide made of fluorine-containing polyimide, but it is disclosed that an adhesive layer needs to be provided in order to improve adhesion to a substrate. Accordingly, there has been a demand for a fluorine-containing polymer that exhibits characteristics such as low dielectric properties and high transparency while maintaining a high fluorine content and maintaining adhesion.
Japan Polyimide Study Group "Latest Polyimide-Basics and Applications-" P269-283 (2002) Nitto Technical Report, 28 (2), 49, (1990) Japanese Patent Laid-Open No. 2001-100055

  The present invention has been made in view of the above problems, and has low dielectric properties, high transparency, high solubility in an alkaline aqueous solution and an organic solvent used as a developer, and high adhesion to a substrate. To provide a fluorine-containing polymer that exhibits characteristics such as low dielectric properties and high transparency while maintaining high fluorine content and maintaining adhesion, in order to achieve high properties and high film-forming properties. .

In order to solve the above-mentioned problems, the present inventors diligently studied the development of a new diamine. As a result, they found a new monomer for introducing a hexafluoroisopropanol group into the same molecule, and studied various polymers thereof. In this way, unprecedented decrease in dielectric constant, improved transparency, and high solubility in alkaline aqueous solutions and organic solvents used as a developer, high adhesion to substrates, and high film-forming properties, The present invention has been completed. Since the hexafluoroisopropanol group-containing polymer used in the present invention contains fluorine and a hydroxyl group, it is possible to exhibit characteristics such as low dielectric property and high transparency while maintaining adhesion. It is an object of the present invention to provide a novel hexafluoroisopropanol group-containing diamine, or a derivative thereof, and further a polymer and an acid labile compound using the hexafluoroisopropanol group-containing diamine or derivative thereof. It is a fluorine-containing diamine represented by these.

  The present invention also relates to a diamine represented by formula (1) and a general formula (2)

Or a tetracarboxylic acid represented by the general formula (3)

A polymer obtained by reacting tetracarboxylic dianhydride represented by the general formula (4):

(Wherein R is a tetravalent organic group containing an aromatic ring, and the carbonyl carbon is bonded to the aromatic ring of R in the ortho position so as to form an imide five-membered ring). Polyamic acid and general formula (5) obtained by dehydrating it

(Wherein, R is the same as the general formula (4)).

  The present invention also relates to a diamine represented by formula (1) and a general formula (6).

Wherein R ¹ is a divalent organic group containing an aromatic ring. X is an —OH group, a halogen (fluorine, chlorine, bromine or iodine) atom or —OR ′ group, and R ′ is an alkyl group or a phenyl group. A polymer obtained by reacting with one selected from dicarboxylic acids, dicarboxylic acid halides and dicarboxylic acid diesters represented by general formula (7):

(In the formula, R ¹ is the same fluorine-containing polyamide resin as the structural unit represented by the general formula (6)).

  According to the present invention, a novel fluorine-containing polyimide or its precursor fluorine-containing polyamic acid that exhibits characteristics such as low dielectric properties and high transparency while maintaining a high fluorine content and maintaining adhesion, and their weight Coalition can be provided.

  The present invention is described in detail below.

  The present invention relates to a hexafluoroisopropanol group-containing diamine represented by the formula (1) (hereinafter referred to as fluorine-containing diamine (1)) and its application. Further, the present invention relates to a polymer or an acid labile compound using the fluorine-containing diamine (1) as a starting material. The production method of the fluorine-containing diamine (1) of the present invention is not particularly limited, but for convenience, 3,5-dinitrobenzoyl chloride and the formula (8)

Can be produced by the condensation reaction and reduction of the nitro group.

  For example, in the condensation reaction between 3,5-dinitrobenzoyl chloride and the compound represented by the formula (8), a method in which both raw materials are dissolved in an organic solvent and reacted, or both raw materials are dissolved (melted) with each other and dissolved. A method of reacting with a solvent is employed. Preferably, the reaction is carried out in the presence of an equimolar number of both raw materials in a temperature range of -20 to 80 ° C in an organic solvent and 100 to 250 ° C in the absence of a solvent. If the temperature is lower than these temperature ranges, the reaction does not proceed, and if it is higher, side reactions tend to occur. In this condensation reaction, 3,5-dinitrobenzoic acid can be used in place of 3,5-dinitrobenzoyl chloride.

  In the reduction reaction of the nitro group of the nitro compound obtained by the condensation reaction, a catalytic hydrogenation method using hydrogen gas or a chemical hydrogenation method usually using a metal and an acid is employed. Preferably, a method in which hydrogen gas is brought into contact with each other in the temperature range of 20 to 100 ° C. in an organic solvent in the presence of a nitro compound and a palladium or platinum catalyst is mentioned.

  The organic solvent used in these condensation reaction and reduction reaction is not particularly limited as long as the raw material or the reaction product is dissolved. N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), 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, butyl acetate, ethyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, acetic acid Chill, 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, methanol, xylene, toluene , Chlorobenzene, terpenes, mineral spirits, petroleum naphtha solvents and the like can be used without any particular limitation.

  The polymer according to the present invention is produced using the fluorine-containing diamine represented by the formula (1) or a derivative thereof, and the polymer is not particularly limited, but is a polyimide, polyamide, polyamine, polyurea and a precursor thereof. Examples thereof include a copolymer in which several kinds of condensation reactions such as polyamide acid, polyamideimide, and polyesterimide are used in combination. Among these, polyimide can be expected to have a wide range of applications as an electronic material and an optical material having high heat resistance.

  The method for producing the fluoropolymer of the present invention is not particularly limited, but an amide, ester and ether-forming derivative synthesized from the fluorodiamine (1) is used as a monomer and can be reacted with its reactive functional group. Polymerized by a mechanism such as condensation, addition polymerization or polyaddition. Accordingly, when synthesizing polyester and polyether, a diol compound is used as a counter monomer, and when synthesizing polyamide, a diamine compound is used as a counter monomer. The structure of these counter monomers that can be used in the present invention is not particularly limited, and known compounds can be used.

  When the fluorine-containing diamine (1) or its amide-forming derivative is used as a raw material in the production of the fluorine-containing polyimide and fluorine-containing polyamide of the present invention, it is possible to copolymerize other amine components or its amide-forming derivatives. It is. The diamine compound that can be used in combination is not particularly limited. Specifically, 3,5-diaminobenzotrifluoride, 2,5-diaminobenzotrifluoride, 3,3′-bistrifluoromethyl-4,4′-diamino Biphenyl, 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-amino Tetrafluorophenoxy) 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- Minophenoxy) 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-bi (4- (3-amino-5-trifluoromethylphenoxy) phenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoro Propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 4,4′-bis (4-amino) Phenoxy) octafluorobiphenyl, 4,4′-diaminobenzanilide and the like. Two or more of these diamine compounds can be used in combination.

  The fluorine-containing polyamic acid of the present invention has the general formula (4) (wherein R is a tetravalent organic group containing an aromatic ring, and the carbonyl carbon is mutually bonded to the aromatic ring of R so as to form an imide five-membered ring. It is bonded to the ortho position.).

  In addition, the fluorine-containing polyimide in the present invention is represented by the general formula (5) (wherein R is a tetravalent organic group containing an aromatic ring, and the carbonyl carbon is a fragrance of R so as to form an imide five-membered ring. And a fluorine-containing polyimide containing a structural unit represented by the following formula:

  The fluorine-containing polyimide of the present invention is composed of a structural unit represented by the general formula (5) or a polymer having the structural unit in the range of 1 to 100 mol%. When the constitutional unit represented by the general formula (5) is 1 mol% or less, the dielectric constant of the film obtained therefrom is not sufficiently low, which is not preferable.

  R in the general formula (4) or (5) is not particularly limited as long as it is a tetravalent organic group containing an aromatic ring.

Or the group shown with the following general formula can be illustrated.

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 optionally substituted with a C ₁ -C ₅ lower alkyl group, or a halogen atom such as chlorine, bromine or fluorine. Here, those in which m is 0 and n is 1 are particularly preferred, and examples thereof include a substituent of the general formula (3). The benzene ring in these general formulas may be optionally substituted with a C ₁ -C ₅ lower alkyl group, or a halogen atom such as chlorine, bromine or fluorine.

  The structure of the tetracarboxylic dianhydride that can be used in the present invention is not particularly limited. For example, trifluoromethylbenzenetetracarboxylic dianhydride, bistrifluoromethylbenzenetetracarboxylic dianhydride, difluorobenzenetetracarboxylic Acid dianhydride, biphenyltetracarboxylic dianhydride, terphenyltetracarboxylic dianhydride, hexafluoroisopropylidenediphthalic dianhydride, oxydiphthalic dianhydride, bicyclo (2,2,2) oct-7 -Ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) fexafluoropropanoic dianhydride (6FDA) and the like.

  The fluorine-containing polyimide of the present invention and the fluorine-containing polyamic acid which is a precursor thereof can be produced by reacting the diamine component with the tetracarboxylic dianhydride. The method and conditions for this polymerization reaction are not particularly limited. For example, a method in which the diamine component and the tetracarboxylic dianhydride are dissolved (melted) with each other in a temperature range of 100 to 250 ° C., preferably 150 to 200 ° C., and reacted without a solvent, or in a high temperature in an organic solvent ( 100-250 ° C., preferably 150-200 ° C.), a polyimide with almost or completely ring closure is obtained. In addition, the diamine component and the tetracarboxylic dianhydride are reacted in an organic solvent at a temperature of -20 to 80 ° C., so that the ring is not closed or only partially closed (4) The method of obtaining the precursor fluorine-containing polyamic acid represented by these is employ | adopted.

  The precursor fluorine-containing polyamic acid or partially ring-closed imide is an acid anhydride such as acetic anhydride, propionic anhydride, benzoic anhydride or the like at a temperature range of 100 to 350 ° C., preferably 250 to 300 ° C. It is possible to obtain a polyimide by adding a ring closing catalyst such as a product, dicyclohexylcarbodiimide, and a ring closing catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, and imidazole as appropriate.

  In these polymerization reactions, a diester dicarboxylic acid derivative obtained by ring-opening the tetracarboxylic dianhydride with an alcohol and a dihalide derivative thereof can also be polymerized with the diamine. In particular, the polyimide precursor in this case is a polyamic acid ester, which is superior to polyamic acid in terms of long-term storage stability.

The fluorine-containing polyamide of the present invention is a polymer compound containing a structural unit represented by the general formula (7) (wherein R ¹ is a divalent organic group containing an aromatic ring).

R ¹ in the general formula (7) is not particularly limited as long as it is a divalent organic group containing an aromatic ring.

Or the group shown with the following general formula can be illustrated.

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} - a and, m is an integer of 1 to 3. The benzene ring in these general formulas may be optionally substituted with a C ₁ -C ₅ lower alkyl group, or a halogen atom such as chlorine, bromine or fluorine. The benzene ring in these general formulas, optionally, a lower alkyl group of C ₁ -C _5, chlorine, bromine, optionally substituted by halogen atoms such as fluorine.

The structure of the dicarboxylic acid, dicarboxylic acid dihalide, and dicarboxylic acid diester represented by the general formula (6) that can be used in the present invention is not particularly limited, but generally known corresponding compounds can be widely used. Examples of the halogen atom used in the dicarboxylic acid dihalide include fluorine, chlorine, bromine and iodine atoms. In particular, dicarboxylic acid dichloride and dicarboxylic acid dibromide using chlorine and bromine atoms are preferably used. Although not particularly limited 'radicals R' -OR is used in the dicarboxylic acid diester, methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an alkyl group of C ₁ -C _10, such as a nonyl group, Examples thereof include a phenyl group substituted with an alkyl group such as a methyl group or an ethyl group, or an unsubstituted phenyl group. In particular, a dicarboxylic acid dimethyl ester, a dicarboxylic acid diethyl ester, or a dicarboxylic acid diphenyl using a methyl group, an ethyl group, or a phenyl group. Esters are preferably used.

  More specifically, for example, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, 3 , 3′-dicarboxyldiphenyl ether, 3,4′-dicarboxyldiphenyl ether, 4,4′-dicarboxyldiphenyl ether, 3,3′-dicarboxyldiphenylmethane, 3,4′-dicarboxyldiphenylmethane, 4,4′-dicarboxyl Diphenylmethane, 3,3′-dicarboxyldiphenyldifluoromethane, 3,4′-dicarboxyldiphenyldifluoromethane, 4,4′-dicarboxyldiphenyldifluoromethane, 3,3′-dicarboxyldiphenylsulfone, 3,4′- Dicarboxyl Phenylsulfone, 4,4'-dicarboxyldiphenylsulfone, 3,3'-dicarboxyldiphenyl sulfide, 3,4'-dicarboxyldiphenyl sulfide, 4,4'-dicarboxyldiphenyl 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) hexafluoropropyl Bread, 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-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) hexafluoropropa 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) terephthalic acid, 4-methoxy-5- ( Perfluorononenyloxy) -containing dicarboxylic acid such as perfluorononenyloxy) isophthalic acid, 5- (perfluorohexenyloxy) isophthalic acid, 4- (perfluorohexenyloxy) phthalic acid, 2- (perfluorohexenyloxy) ) Terephthalic acid, 4-methoxy-5- (perf) Oro hexenyloxy) perfluoroalkyl hexenyl group-containing dicarboxylic acids such as isophthalic acid, aromatic dicarboxylic acids and dicarboxylic acid dihalide corresponding to each of these carboxylic acids and the like, dicarboxylic acid diester can be exemplified. That is, dicarboxylic acid dihalides such as dichloride and dibromide of the corresponding dicarboxylic acid, dicarboxylic acid dialkyl esters such as dimethyl ester and diethyl ester, and dicarboxylic acid diphenyl ester. These may be used alone or in combination of two or more.

  The fluorine-containing polyamide of the present invention can be produced by reacting the fluorine-containing diamine component represented by the formula (1) with the dicarboxylic acid, dicarboxylic acid dihalide or dicarboxylic acid diester represented by the general formula (6). . The method and conditions for this polymerization reaction are not particularly limited. For example, a method of dissolving (melting) the diamine component and the amide-forming derivative of the dicarboxylic acid in a temperature range of 100 to 250 ° C., preferably 150 to 200 ° C., and reacting them in the absence of a solvent, or a high temperature in an organic solvent. (The temperature range is 100 to 250 ° C., preferably 150 to 200 ° C.), and the method is a method of reacting in an organic solvent at a temperature of −20 to 80 ° C.

  The organic solvent that can be used for the polymerization reaction of the fluorine-containing polymer (fluorine-containing polyamic acid, fluorine-containing polyamide, and fluorine-containing polyimide) according to the present invention is not particularly limited as long as both components of the raw material dissolve, but N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), 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 Such as 2-imidazolidinone can be used. Furthermore, as long as the solubility of both raw material components is not impaired, other organic solvents such as 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, terpene , Mineral spirits, petroleum naphtha solvents and the like can be used without particular limitation.

  As a post-treatment method after the polymerization reaction of the fluorine-containing polymer (fluorine-containing polyamic acid, fluorine-containing polyamide and fluorine-containing polyimide) according to the present invention, a precipitation method is employed. The solvent is not particularly limited as long as the unreacted raw material monomer is dissolved and the fluoropolymer is precipitated, but butyl acetate, ethyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethyl 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, methanol, isopropyl alcohol, hexane, xylene, Use toluene, chlorobenzene, terpenes, mineral spirits, petroleum naphtha solvents, etc. That.

  The fluorine-containing polymer (fluorine-containing polyamic acid, fluorine-containing polyamide, and fluorine-containing polyimide) in the present invention, each dissolved in dimethylacetamide (DMAc), is dissolved in the solvent at a concentration of 0.1 g / dl, The reduced viscosity measured at 30 ° C. with an Ostwald viscometer is preferably 0.01 dl / g or more, particularly preferably 0.3 dl / g or more. In producing the fluoropolymer film, a reduced viscosity of 0.01 dl / g or more is preferable for maintaining the shape, and particularly 0.3 dl / g or more is preferable for ensuring strength.

  The fluorine-containing polymer (fluorine-containing polyamic acid, fluorine-containing polyamide and fluorine-containing polyimide) of the present invention can be used in a varnish state dissolved in an organic solvent, or in a powder state, a film state or a solid state. When using in varnish, apply it on a substrate such as glass, silicon wafer, metal, metal oxide, ceramics, resin, etc. by usual methods such as spin coating, spray coating, flow coating, impregnation coating, brush coating. Can do.

In terms of electronic material applications, it is effective to reduce the dielectric constant of the material in order to reduce the signal delay in the semiconductor element, and to align the thermal expansion coefficient of the material in order to prevent cracks at the interface between different materials (organic materials are Since the expansion coefficient is larger than that of the inorganic material, it is effective to make the thermal expansion coefficient uniform for the organic material). In particular, the hexafluoroisobropanol group-containing polyimide in the present invention is excellent in that it has both the above-described properties of lowering the dielectric constant and lowering the thermal expansion coefficient, and also has solubility in an alkaline aqueous solution.
"Example"
Examples of the present invention will be described below, but the present invention is not limited to these examples.

  20.00 g of the compound of formula (8), 10.82 g of 3,5-dinitrobenzoyl chloride, 4.6 ml of pyridine, and 150 ml of methylene chloride are added to a 300 ml three-necked flask, and the mixture is kept at 40 ° C. for 3 hours under a nitrogen atmosphere. Stir. The reaction solution was poured into a 0.6 N HCl aqueous solution, and the resulting white precipitate was collected by filtration and then vacuum dried at room temperature. 20.97 g (yield 72%) of white powder was obtained. The NMR spectrum suggested the structure of formula (9) shown below. The NMR spectrum is shown in FIG.

  9.90 g of the compound obtained in Example 1 (formula (9)), 0.97 g of 10% -palladium carbon, and 75 ml of N, N-dimethylformamide (DMF) were added to a 300-ml three-necked flask, and hydrogen was added. It was equipped with a balloon and stirred at room temperature for 12 hours. The reaction mixture was treated with celite, the obtained filtrate was poured into water, and the resulting precipitate was recovered. Recrystallization purification was performed using a mixed solvent of methanol and water to obtain 5.13 g (yield 57%) of white powder. The NMR spectrum indicated the structure of formula (1) shown below. The NMR spectrum is shown in FIG.

1.50 g of the fluorinated diamine (formula (1)) obtained in Example 2, 1.19 g of 6FDA (2,2-bis (3,4-dicarboxyphenyl) fexafluoropropanoic acid dianhydride) and N , N-dimethylacetamide (DMAc) (10.8 ml) was charged into a 100-ml three-necked flask equipped with a stirrer and stirred at room temperature for 5 hours under a nitrogen stream. The reaction solution was poured into a mixed solvent of methanol and water to precipitate the polymer. The precipitated polymer was separated by filtration and vacuum dried at 50 ° C. to obtain 2.50 g (95% yield) of fluorinated polypolyamic acid. It was dissolved in DMAc at a concentration of 0.1 g / dl, and the intrinsic viscosity measured at 30 ° C. with an Ostwald viscometer was 0.44 dl / g. When the structure of the obtained polyamic acid was confirmed by IR and ¹ H-NMR spectrum, it was suggested to be the following formula (10). ^{The 1} H-NMR spectrum is shown in FIG.

When the polymer (formula (10)) obtained in Example 3 was dissolved in dimethylacetamide (DMAc) and spread on a glass plate and heat-treated at 250 ° C., a highly transparent and tough film was obtained. It was. From the IR spectrum of the obtained film, the structure was found to be the following fluorine-containing polyimide (formula (11)). When the dielectric constant of the obtained fluorine-containing polyimide film was measured, it was 2.5 at 1 MHz. When the linear thermal expansion coefficient of this film was measured, it was 4 * 10 < ^-5 > / degreeC as an average value of 50-300 degreeC. The film was dissolved in a 2.38 wt% tetramethylammonium aqueous solution.

0.50 g of the polyamic acid (formula (10)) obtained in Example 3, 0.10 g of pyridine, 0.13 g of acetic anhydride, and 4.5 g of DMF were added to a 100 ml three-necked flask, and the mixture was heated to 110 ° C. under a nitrogen atmosphere. And stirred for 12 hours. The reaction solution was poured into a mixed solvent of methanol and water to precipitate the polymer. The precipitated polymer was separated by filtration and vacuum dried at 100 ° C. to obtain 0.43 g (90% yield) of fluorine-containing polyimide. From structural analysis by IR and ¹ H-NMR spectrum, it was found that the obtained polyimide had a chemical structure of the formula (11). It was dissolved in DMAc at a concentration of 0.1 g / dl, and the intrinsic viscosity measured at 30 ° C. with an Ostwald viscometer was 0.30 dl / g. The obtained IR spectrum is shown in FIG. The fluorine-containing polyimide obtained by the chemical imidization (formula (11)) is not only DMF and DMAc, but also low-boiling organic solvents such as acetone, methanol, tetrahydrofuran, propylene glycol monomethyl ether acetate, and 2.38 wt% tetra Good solubility in methylammonium aqueous solution was also exhibited.

1.50 g of the diamine (formula (1)) obtained in Example 2, 1.15 g of 2,2-bis (3-carboxyphenyl) hexafluoropropane) acid dichloride, N, N-dimethylacetamide (DMAc) 10.8 ml was charged into a 100 ml three-necked flask equipped with a stirrer and stirred at room temperature for 5 hours under a nitrogen stream. The reaction solution was poured into a mixed solvent of methanol and water to precipitate the polymer. The precipitated polymer was separated by filtration and vacuum dried at 100 ° C. to obtain 2.38 g (yield 95%) of a fluorine-containing polyamide (formula (12)). It was dissolved in DMAc at a concentration of 0.1 g / dl, and the intrinsic viscosity measured at 30 ° C. with an Ostwald viscometer was 0.40 dl / g. The structure of the obtained polyamic acid was confirmed by IR and ¹ H-NMR spectrum.

  The fluoropolymer of the present invention has a low dielectric constant and a low thermal expansion coefficient while maintaining properties such as mechanical strength and thermal stability, and also exhibits good solubility in an organic solvent and an alkaline aqueous solution as a developer. Therefore, it is useful as an insulating material for electrical / electronic parts and a coating material for optical parts.

2 is a ¹ H-NMR spectrum of a dinitro compound (formula (9)) obtained in Example 1. FIG. 2 is a ¹ H-NMR spectrum of a fluorine-containing diamine (formula (1)) obtained in Example 2. 2 is a ¹ H-NMR spectrum of the fluorine-containing polyamic acid obtained in Example 3 (formula (10)). 4 is an infrared absorption spectrum of the fluorine-containing polypolyimide (formula (11)) obtained in Example 5.

Claims (6)

A fluorine-containing diamine represented by the formula (1).

Diamine represented by formula (1) and general formula (2)

Or a tetracarboxylic acid represented by the general formula (3)

A polymer obtained by reacting tetracarboxylic dianhydride represented by the general formula (4):

(Wherein R is a tetravalent organic group containing an aromatic ring, and the carbonyl carbon is bonded to the aromatic ring of R in the ortho position so as to form an imide five-membered ring). Polyamic acid. A polymer obtained by dehydrating a fluorine-containing polyamic acid represented by the general formula (4), the polymer having the general formula (5)

(In the formula, R is the same as the general formula (4)). R is the following formula

(In the formula, each aromatic ring has a dangling bond at the ortho position with respect to each other, and the hydrogen atom of the aromatic ring may be substituted with a halogen (fluorine, chlorine, bromine or iodine) atom). The fluorine-containing polyimide resin according to claim 3, which is a group. Diamine represented by general formula (1) and general formula (6)

Wherein R ¹ is a divalent organic group containing an aromatic ring. X is an —OH group, a halogen (fluorine, chlorine, bromine or iodine) atom or —OR ′ group, and R ′ is an alkyl group or a phenyl group. A polymer obtained by reacting with one selected from dicarboxylic acids, dicarboxylic acid halides and dicarboxylic acid diesters represented by general formula (7):

(In the formula, R ¹ Formula (6)) to the fluorine-containing polyamide resin containing a structural unit represented by. R ¹ represents the following formula

6. The fluorine-containing polyamide resin according to claim 5, which is an organic group represented by the formula (wherein the hydrogen atom of the aromatic ring may be substituted with a halogen (fluorine, chlorine, bromine or iodine) atom).

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