TWI694989B - Tetracarboxylic dianhydride having cyclic hydrocarbon skeleton and ester group - Google Patents

Abstract

Polyimide having excellent solvent solubility, dielectric constant and transparency can be produced from tetracarboxylic dianhydride having a cyclic hydrocarbon skeleton and an ester group as shown in the following formula (1)

(In the formula, x represents an integer of 1 to 11, and R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, a cycloalkyl group having 4 to 16 carbon atoms, or a carbon number Aromatic groups of 6 to 12. When R ₁ and/or R ₂ exist in plural, they may be the same or different from each other. m and n each independently represent an integer of 0 or 1 to 4.).

Description

Tetracarboxylic dianhydride with cyclic hydrocarbon skeleton and ester group

The present invention relates to a novel tetracarboxylic dianhydride having a cyclic hydrocarbon skeleton and an ester group that can be used as a raw material for polyimide resins, etc., polyamic acid and polyacrylic acid obtained from the tetracarboxylic dianhydride Imine.

The tetracarboxylic dianhydride is used as a raw material for the polyimide resin in addition to the hardener for the epoxy resin and the polyurethane resin. Especially because polyimide has excellent heat resistance, it also has mechanical properties, electrical properties, and chemical resistance, and is used as a flexible printed wiring circuit in the field of electrical and electronic materials, especially semiconductor electronic materials. Substrates, interlayer insulating films, and protective films are widely used. However, because most polyimides are insoluble in organic solvents, it is generally not easy to shape and process the polyimides themselves. Therefore, polyimide is formed into a film or the like in the state of a polyamic acid solution as its precursor, and it is necessary to perform a heating dehydration ring-closing reaction (amidation) at a so-called high temperature of 250 to 350°C. However, as the density of electronic circuits has increased, the use of multilayer wiring boards has resulted in the cooling of the polyimide/metal substrate laminate from the thermal imidization temperature (250 to 350°C) to room temperature. Thermal stress generated during the process often causes problems such as curling, peeling, and cracking of the film, and causes a problem that the reliability of the device is significantly reduced.

On the other hand, in the case where polyimide is dissolved in an organic solvent, a solvent solution (varnish) of polyimide is coated on the metal substrate, and only a temperature lower than the thermal imidization temperature is used and The solvent can be formed by evaporating and drying, and finally, the polyimide/metal substrate layer can be reduced Under the premise of thermal stress in the body, seek solvent soluble polyimide.

At the same time, the processing speed of devices such as LSI (Large Scale Integrated Circuit) is expected to be further increased. One of the methods to support this speeding up is to use a low dielectric constant interlayer insulating film covering the periphery of the wiring, and use polyimide with excellent heat resistance as the interlayer insulating film, but the typical dielectric of polyimide The constant is 3.5 to 3.0, and the dielectric constant is expected to further decrease.

Furthermore, in recent years, the use of high-transparency polyimide has been discussed in light waveguides proposed as a new generation of surface-mount substrates on the premise of good heat resistance. Once high transparency is available, If the polyimide has heat resistance, solubility, and moderate toughness, the polyimide can be used as an alternative material for glass substrates used in liquid crystal displays, electronic paper, and solar cells.

As such a polyimide having solvent solubility, low dielectric constant, high transparency and high heat resistance, for example, an ester that can be produced from 9,9-bis(4-hydroxyphenyl)fluorene Bonded tetracarboxylic dianhydrides are widely known as polyimide systems produced by reaction with amines such as 4,4'-diaminodiphenyl ether (4,4'-ODA, Oxydianiline) (Patent Document 1). However, polyimide is still sought to further improve solvent solubility, low dielectric constant, and transparency.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-open Publication "JP-A-2007-91701".

The object of the present invention is to provide a low dielectric constant, high transparency, and high Solvent-soluble polyimide.

The inventors focused on the structure of tetracarboxylic dianhydride in the raw materials of polyimide and repeated careful research, and found that by combining tetracarboxylic dianhydride and diamines having a cyclic hydrocarbon skeleton and an ester group The polyimide obtained by polymerization can produce polyimide which has the characteristics of so-called low dielectric constant and high transparency, and also has the characteristics of high solubility in organic solvents, and finally completed the present invention. That is, the present invention provides the following compounds [1] to [3].

A tetracarboxylic dianhydride characterized by the following formula (1).

(In the formula, x represents an integer of 1 to 11, and R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, a cycloalkyl group having 4 to 16 carbon atoms, or a carbon number Aromatic groups of 6 to 12. When R ₁ and/or R ₂ are present in plural, they may be the same or different from each other. m and n each independently represent an integer of 0 or 1 to 4.)

[2]

A polyamide having a repeating unit represented by the following formula (2).

[Chem 2]

(In the formula, the meaning represented by x, R ₁ , R ₂ , m, and n is as shown above. Meanwhile, Z represents a diamine residue.)

[3]

A polyimide characterized by having a repeating unit represented by the following formula (3).

(In the formula, the meanings represented by x, R ₁ , R ₂ , m, n, and Z are as shown above.)

By polymerizing tetracarboxylic dianhydride and diamines having a cyclic hydrocarbon skeleton and an ester group discovered in the present invention, it is possible to produce the so-called low dielectric constant, high transparency, and high organic solvents. Polyimide with solubility characteristics. This polyimide has the characteristics of so-called low dielectric constant, high transparency, and high solubility in organic solvents, so it can be applied to the interlayer between flexible printed circuit boards, protective films for semiconductor elements, and integrated circuits. Electronic materials such as insulating films, optical communication materials such as optical fibers and optical waveguides, and their use as flexible substrates instead of glass substrates commonly used in liquid crystal displays, electronic paper, and solar cells.

1 is a ¹ H-NMR spectrum of tetracarboxylic dianhydride having a structure represented by the following formula (1-A) in the tetracarboxylic dianhydride represented by the above formula (1).

[FIG. 2] FIG. 2 is a ¹³ C-NMR spectrum of tetracarboxylic dianhydride having a structure represented by the following formula (1-A) in the tetracarboxylic dianhydride represented by the above formula (1).

[Fig. 3] Fig. 3 is a mass spectrum of tetracarboxylic dianhydride having a structure represented by the following formula (1-A) in the tetracarboxylic dianhydride represented by the above formula (1).

<Tetracarboxylic dianhydride with novel cyclic hydrocarbon skeleton and ester group>

Hereinafter, the present invention and its embodiments will be described together. In the present invention, the tetracarboxylic dianhydride having a cyclic hydrocarbon skeleton and an ester group is represented by the following formula (1).

(In the formula, x represents an integer of 1 to 11, and R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, a cycloalkyl group having 4 to 16 carbon atoms, or a carbon number Aromatic groups of 6 to 12. When R ₁ and/or R ₂ exist in plural, they may be the same or different from each other. m and n each independently represent an integer of 0 or 1 to 4.).

In the chemical structure represented by the above formula (1), the number X of alkylene groups representing the cyclic hydrocarbon skeleton is an integer of 1 to 11. Specifically, the alkylene system of the cyclic hydrocarbon skeleton represents cyclooctyl, cyclononyl, and cyclo Decyl, ring undecyl, ring dodecyl, ring thirteen, ring fourteen, ring fifteen, ring sixteen, ring seventeen, ring eighteen. From the viewpoint of availability of raw materials, cyclooctyl, cyclodecyl, cyclododecyl, cyclopentadecyl are preferred, and cyclododecyl is more preferred.

In the above formula (1), R ₁ and R ₂ independently represent an alkyl group having 1 to 12 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl Straight-chain or branched alkyl groups such as alkyl, sec-butyl, tert-butyl, pentyl, and hexyl. The alkyl group having 1 to 12 carbon atoms is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and particularly preferably It is a linear or branched alkyl group having 1 to 3 carbon atoms. As for the cycloalkyl group having 4 to 16 carbon atoms, for example, for example, cyclopentyl group, cyclohexyl group, alkyl group (for example, C 1 to 4 alkyl group) substituted cyclopentyl group, alkyl group (for example , A cycloalkyl group such as a cyclohexyl group substituted with 1 to 4 carbon atoms, a cycloalkyl group having 4 to 16 carbon atoms (preferably 5 to 8 carbon atoms), or a cycloalkyl group substituted with an alkyl group. The cycloalkyl system is preferably cyclopentyl or cyclohexyl. Examples of the aromatic groups having 6 to 12 carbon atoms include, for example, phenyl groups and naphthyl groups substituted with phenyl groups and alkyl groups (for example, alkyl groups having 1 to 4 carbon atoms). The aromatic group is preferably phenyl or alkyl-substituted phenyl (for example, methylphenyl, dimethylphenyl, ethylphenyl, etc.), more preferably phenyl. As for the halogen atom, fluorine, chlorine, bromine and the like are exemplified, and preferably chlorine or bromine.

The number of substituents R ₁ and R ₂ represented by m and n is 0 or an integer of 1 to 4, preferably 0, 1, or 2. Although m and n may be the same or different, they are usually the same.

Regarding R ₁ and R ₂ in the above formula (1) detailed above, from the viewpoint of whether it is easy to obtain the cyclic hydrocarbon skeleton compound represented by the following formula (4) as a raw material, among these substituents , Preferably: the number of substituents is 1 (m=n=1) and the substituents are methyl, ethyl, phenyl; the number of substituents is 2 (m=n=2) and all of the substituents Is methyl; or there is no substituent, meaning m=n=0. In particular, it is preferred that the number of substituents is one and the substituent is methyl, or there is no substituent.

The tetracarboxylic dianhydride represented by the above formula (1) is not only used as a raw material for polyimide, but also It can be used as raw materials for resins and additives such as polyester, or as hardeners for epoxy resins and polyurethane resins.

<Production method of tetracarboxylic dianhydride represented by the above formula (1)>

In the present invention, a known method can be suitably used as a method for obtaining the tetracarboxylic dianhydride represented by the above formula (1). For example, in the presence of a deoxidizer (alkali), the following formula (4)

(In the formula, the meanings represented by x, R ₁ , R ₂ , m, n, and Z are as shown above.) 1,1-bis(4-hydroxyphenyl) cycloalkanes (hereinafter also referred to as Is a method of reacting acid halide of trimellitic anhydride with bisphenol naphthenes (acid halide method), directly dehydrating the bisphenol naphthenes and trimellitic anhydride represented by the above formula (4) Method, a method for deacetic acid reaction of the diacetate of bisphenol naphthenes represented by the above formula (4) with trimellitic anhydride at high temperature, dehydration using dicyclohexylcarbodiimide, etc. A method for dehydrating and condensing bisphenol naphthenes and trimellitic anhydride represented by the above formula (4), using tosyl chloride/N,N-dimethylformamide/pyridine The method of activating trimellitic anhydride to esterify the bisphenol naphthenes represented by the above formula (4), etc. Among these, since the acid halide method can obtain trimellitic acid halide as a raw material at a low price, the acid halide method is preferable. The acid halide method will be described in detail below.

Specifically, the acid halide method system means that, in the presence of a deoxidizer, the acid halide of bisphenol naphthenes represented by the above formula (4) and trimellitic anhydride represented by the following formula (7) The reaction to obtain the tetracarboxylic dianhydride represented by the above formula (1) (hereinafter, this reaction is also referred to as an esterification reaction). Furthermore, the bisphenol naphthenes represented by the above formula (4) correspond to the tetracarboxylic acid represented by the above formula (1) The cyclic hydrocarbon skeleton structure of acid dianhydride.

The bisphenol naphthenic system represented by the above formula (4) used as a raw material can be a commercially available product and can be produced using a well-known method (for example, Japanese Laid-Open Patent Publication "JP 2010-248164 Gazette", Japan (Public Patent Gazette "Special Publication 2011-6337 Gazette", etc.). Specifically, this manufacturing method uses an acid catalyst and, if necessary, in the presence of thiols, the cyclic ketones represented by the following formula (5)

(In the formula, the meaning represented by x is as shown above.) It is obtained by reacting with a phenol represented by the following formula (6).

(In the formula, R ₃ independently represents an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, a cycloalkyl group having 4 to 16 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. In R ₃ When plural numbers exist, they may be the same or different from each other. k represents 0 or an integer of 1 to 4.) Furthermore, the phenols represented by the above formula (6) may be used in combination of two or more as necessary.

The acid halide of trimellitic anhydride used in the esterification reaction has a structure represented by the following formula (7).

[Chem 8]

(Y is a halogen atom.)

Since the acid chloride of trimellitic anhydride can be obtained at a low price, it is expected that Y is a chlorine atom.

Generally, the amount of acid halide of trimellitic anhydride represented by the above formula (7) used for the esterification reaction is 1 to 4 with respect to 1 mol of the bisphenol naphthenes represented by the above formula (4). Times mole, preferably 2.2 to 2.6 times mole. Once the amount of trimellitic anhydride acid halide used is less than 2 times the molar amount, the reaction cannot proceed sufficiently. When it is more than 4 times mole, it will remain in the reaction system as an impure substance, and the purity of the obtained tetracarboxylic dianhydride represented by the above formula (1) decreases.

For the deoxidizer used in the esterification reaction, for example, organic tertiary amines such as pyridine, triethylamine, N,N-dimethylaniline, propylene oxide, allyl glycerol Epoxy (Allyl Glycidyl Ether) and other inorganic salts such as potassium carbonate and sodium hydroxide. One type of these deoxidizers may be used, or two or more types may be used together as necessary. Among these deoxidizers, pyridine is more suitable from the viewpoint of manufacturing cost and ease of separation. The deoxidizer is generally used in an amount of 2 to 4 times the molar amount, preferably 2 to 3 times the molar amount, relative to 1 mole of the bisphenol cycloalkane represented by the above formula (4). By using the deoxidizing agent in an amount of 2 times or more, the reaction speed can be improved, and by using the deoxidizing agent in a amount of 4 times or less, the generation of impurities can be suppressed.

When carrying out the esterification reaction, an organic solvent may be used as necessary. As for the usable organic solvents, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 1,2-ethylene glycol dimethyl ether, tetrahydrofuran, cyclopentyl Ether solvents such as methyl ether, benzene, toluene, Aromatic hydrocarbons such as xylene and halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene. Ether solvents are preferred. In the case of using an organic solvent, the amount of the organic solvent used is usually 1 to 30 times by weight, preferably 1 to 5 times by weight, relative to 1 time by weight of the bisphenol naphthenes represented by the above formula (4). One type of these organic solvents may be used, or two or more types may be used in combination as necessary.

The reaction temperature during the esterification reaction is usually -10°C to 110°C, preferably -5°C to 80°C, and more preferably 20°C to 70°C. Once the reaction temperature is higher than 110°C, by-products may increase, and once the reaction temperature is lower than -10°C, the reaction may not proceed efficiently.

As for the method of the esterification reaction, for example, the above solvent is mixed while stirring the solution of the acid chloride of trimellitic anhydride represented by the above formula (7) and the above organic solvent. There is a solution of the bisphenol naphthenes represented by the above formula (4) and a deoxidizer, which is added intermittently or continuously to the solution of the acid chloride of the trimellitic anhydride represented by the above formula (7) and the above organic solvent And make the temperature into the above reaction temperature range, and after the addition, the reaction under the above temperature range "esterification reaction."

After the esterification reaction is completed, crystals are precipitated by cooling the product to 15 to 35° C., and by filtering the precipitated crystals, the tetracarboxylic dianhydride represented by the above formula (1) of the present invention can be obtained. If necessary, the obtained tetracarboxylic dianhydride represented by the above formula (1) may be subjected to general purification treatments such as adsorption treatment, recrystallization, or distillation.

Meanwhile, after the esterification reaction is completed, by adding water and an organic solvent to the reaction system and washing with water, the tetracarboxylic dianhydride represented by the above formula (1) of the present invention can be removed from the organic solvent layer After extraction, excess deoxidizer, trimellitic anhydride acid chloride, and deoxidizer halide are removed from the water layer, and then, in the presence of an organic solvent and anhydrous acetic acid, the aforementioned water washing process will be used as a subsidiary The ring-opened body produced by the product (the fourth shown in the above formula (1) (Hydrolyzed product of carboxylic acid dianhydride) After the ring-closing reaction is carried out to make the tetracarboxylic dianhydride represented by the above formula (1) again, the above formula (1) can also be obtained by precipitating and filtering the crystal The tetracarboxylic dianhydride shown. For the obtained tetracarboxylic dianhydride represented by the above formula (1), the same general purification treatment as the above method can be repeated.

From the viewpoint of easily improving the degree of polymerization of the polyamic acid having the repeating unit represented by the above formula (2) or the polyimide represented by the above formula (3), generally, it is measured by the method described later In the HPLC purity meter, the purity of the tetracarboxylic dianhydride represented by the above formula (1) is 95% or more, preferably 99% or more.

<Polyamide having the repeating unit represented by the above formula (2) and its production method>

Next, the polyamic acid having the repeating unit represented by the above formula (2) (hereinafter, also referred to as the polyamic acid of the present invention) will be described in detail. The polyamide of the present invention has a repeating unit represented by the following formula (2).

(In the formula, the meaning represented by x, R ₁ , R ₂ , m, and n is as shown above. Meanwhile, Z represents a diamine residue.)

Furthermore, the diamine residue in the above formula (2) represents the amine group (-NH) of the diamine obtained when the tetracarboxylic dianhydride represented by the above formula (1) is reacted with a diamine described later. ₂ ) Other structures.

The molecular weight of the polyamic acid of the present invention is obtained by the measurement method described below, and In terms of weight average molecular weight, the molecular weight of the polyamic acid of the present invention is preferably 10,000 or more, more preferably 20,000 or more, particularly preferably 40,000 or more, and at the same time, preferably 600,000 or less, more preferably 500,000 Below, Tejia is below 300,000. Once the molecular weight of the polyamic acid is more than 10,000, it can be molded, and it is easy to maintain good mechanical properties. Once the molecular weight of the polyamic acid is less than 600,000, it is easy to control the molecular weight during synthesis, and at the same time, it is often the case that a solution of appropriate viscosity is obtained and therefore easy to handle. In addition, for the molecular weight of the polyamic acid, the viscosity of the polyamic acid solution can be used as a reference.

For the method for producing the polyamic acid of the present invention, for example, after dissolving the diamines described later in a polymerization solvent described later, usually at 10 to 20° C., the above formula (1) of the present invention is added After the powder of tetracarboxylic dianhydride and stirring at 10~100℃, preferably 10~30℃, a solution using polyamic acid as a polymerization solvent (hereinafter, also called polyamic acid solution) can be obtained ).

The diamine that can be used in the present invention is not particularly limited as long as it does not significantly impair the polymerization reactivity of the polyimide precursor and the required performance of the polyimide, and general aromatic Diamine, aliphatic diamine, alicyclic diamine, etc. For such diamines, for example, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether (alias 4,4'-oxydiphenylamine), 3,3'-diaminodiphenylbenzene, 3,4'-diaminodiphenyl Ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'bis(trifluoro Methyl)-4,4'-diaminobiphenyl (alias 2,2'bis(trifluoromethyl)-benzidine), 3,7-diamino-dimethyldibenzothiophene (Benzothiophene) -5,5-Dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis(4-aminophenyl) sulfide Substances, 4,4'-diaminodiphenylbenzene, 4,4'-diaminobenzylanilide, 1,3-bis(4-aminophenoxy)propane, 1,4-bis( 4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,3-bis(4-aminophenoxy)-2,2-dimethyl Propane, 1,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 9,9-bis(4-aminophenyl)fluorene, 5(6)-amino-1 -(4-Aminomethyl)-1,3,3-trimethylindane (indane), 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-amine Phenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-amino Phenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]benzene, bis[4 -(3-Aminophenoxy)phenyl] ash, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 3,3'-dicarboxylic acid-4 ,4'-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylene diamine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 2, 2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3',4,4'tetraaminobiphenyl, 1,6-diaminohexane, 1,3-bis( 3-aminopropyl)tetramethyldisilaxane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4'-methylenebis(4 -Cyclohexylamine), trans 1,4-cyclohexanediamine, bicyclo[2.2.1]heptane bis(methylamine), tricyclo[3.3.1.13.7]decane-1,3-di Amine, 4-aminobenzoic acid-4-aminophenyl ether, 2-(4-aminophenyl)aminobenzoxazole (Benzoxazole), 9,9-bis[4-(4-amino (Phenoxy)phenyl) fluorene, 2,2'-bis(3-sulfopropoxy)-4,4'diaminobiphenyl, 4,4'-bis(4-amino Phenoxy)biphenyl-3,3'-disulfonic acid, etc. At the same time, these can also be used in combination of two or more.

Among these diamines, alicyclics such as 3,3'-diaminodiphenyl sulfone, bicyclo[2.2.1]heptane bis(methylamine), trans 1,4-cyclohexanediamine, etc. are used In the case of family diamines, the transparency of the polyimide obtained is more significantly improved. At the same time, when using 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2 In the case of fluorine-containing diamines such as ,2'-bis(trifluoromethyl)-benzidine, the low dielectricization and solvent solubility of the obtained polyimide can be more significantly improved. In the case where the tetracarboxylic dianhydride represented by the above formula (1) and other acid dianhydrides are used in combination, the total acid anhydride including other acid anhydrides is 1 mole, and generally, such diamines use 0.9 to 1.1 moles, from the viewpoint of improving the degree of polymerization, it is preferable to use 0.95 to 1.05 moles.

At the same time, general acid anhydride can be used as the copolymerization component as necessary. Examples of acid anhydrides that can be used in combination include pyromellitic dianhydride, Oxydiphthalic dianhydride, biphenyl-3,4,3',4'-tetracarboxylic dianhydride Benzophenone-3,4,3',4'-tetracarboxylic dianhydride, dibenzophenone-3,4,3',4'-tetracarboxylic dianhydride, 4,4'-(2, 2-Hexafluoroisopropyl) phthalic dianhydride (4,4'-(2,2-Hexafluoroisopropylidene) diphthalic dianhydride), m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride , P-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic acid Acid dianhydride, 1-carboxymethyl-2,3,5-cyclopentane tricarboxylic acid-2,6: 3,5-dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid di Anhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 4-Phenylethynyl diphthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic acid Dianhydride, bis(1,3-dioxy-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-benzyl ester (bis(1,3-dioxo-1,3 -dihydroisobenzofuran-5-carboxylic acid)1,4-Phenylene), etc., these can also be used in combination of two or more. When other acid anhydrides are used in combination, the use amount of other acid anhydrides in all acid anhydrides is preferably 10% by weight or more, more preferably 30% by weight or more, and on the other hand, preferably 90% by weight or less, more preferably 70 Weight% or less. By using 10% by weight or more of other acid anhydrides, as described later, the effect of sufficiently improving the physical properties can be obtained by using other acid anhydrides in combination. On the other hand, by using other dianhydrides of 90% by weight or less, the effect of the tetracarboxylic dianhydride having a cyclic hydrocarbon skeleton and an ester group represented by the above formula (1) of the present invention can be fully exhibited.

In terms of the effect of using other acid anhydrides together, for example, by using a fluorine-containing dianhydride such as 4,4′-(2,2-hexafluoroisopropylidene)phthalic dianhydride, it is possible to obtain The polyimide becomes lower dielectric constant. At the same time, when acid anhydrides such as pyromellitic dianhydride having a rigid structure are used together, the heat resistance of the obtained polyimide can be further improved.

As for the solvent that can be used in the manufacture of polyamic acid, as long as it can dissolve the tetracarboxylic dianhydride and diamines represented by the above formula (1) of the present invention as the raw material monomers, and for these raw materials and production The polyamic acid is not active and is not particularly limited. As for such a solvent, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. can be used. , Chain ester solvents such as butyl acetate, ethyl acetate, isobutyl acetate, etc., cyclic ester solvents such as γ-butyrolactone, γ-caprolactone, ε-caprolactone, etc. , Carbonic acid solvents such as propylene carbonate, triethylene glycol, ethyl cellosolve, butyl cellosolve, propylene glycol methyl acetate, 2-methyl cellosolve acetate, ethyl cellosolve Glycol series of threoacetate, butylcellulose acetate, dimethoxyethane, diethoxyethane, diethylene glycol, etc. Agents, phenol solvents such as phenol, o-cresol, m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, etc., ether solvents such as tetrahydrofuran, dibutyl ether, diethyl ether, etc. Ketone solvents such as butyl ketone, diisobutyl ketone, cyclopentanone, methyl ethyl ketone, acetone, and acetophenone; alcohol solvents such as butanol and ethanol; xylene, toluene, chlorobenzene, etc. Aromatic solvents, such as dimethyl sulfoxide, ciproline, etc. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-pyrrolidone and the like are preferred. One of these solvents may be used, or two or more may be mixed and used as necessary.

In terms of the amount of the solvent used, the total concentration of the monomer components in the reaction system is usually 5 to 40% by weight, preferably 10 to 25% by weight. By polymerizing in this monomer concentration range, a uniform and high degree of polymerization of polyamide can be obtained. Furthermore, once polymerization is performed at a concentration lower than the above monomer concentration range, the degree of polymerization of polyamic acid cannot be sufficiently high, and the resulting polyimide film may become fragile, however, Once the polymerization is performed at a concentration higher than the above-mentioned monomer concentration range, the monomer may become insufficiently dissolved or the reaction solution may become uneven to cause gelation. Generally, the polyamic acid solution having the repeating unit represented by the above formula (2) obtained by the above method is directly used in the polyimidization process using the method described later.

<Polyimide having the repeating unit represented by the above formula (3) and its production method>

Next, the polyimide having the repeating unit represented by the above formula (3) (hereinafter, also referred to as the polyimide of the present invention) will be described in detail. The polyimide system of the present invention means a polyimide having a repeating unit represented by the following formula (3).

[化10]

(In the formula, the meanings represented by x, R ₁ , R ₂ , m, n, and Z are as shown above.)

The polyimide having the repeating unit represented by the above formula (3) of the present invention can be obtained by subjecting the polyamic acid having the repeating unit represented by the above formula (2) obtained by the above method to a dehydration ring-closure reaction ( Amide imidization reaction). As for the method of the imidate reaction, for example, the thermal imidate method or the chemical imidate method is exemplified.

First, the thermal imidization method will be described in detail. As for the thermal imidate method, for example, a polyamic acid polymerization solution is cast on a glass substrate, and then heated in a vacuum, in an inert gas such as nitrogen, or in air. For example, in general, a film of polyamic acid can be obtained by drying in an oven at 50 to 190°C, preferably 100 to 180°C.

Next, the obtained polyamic acid film is heated on the glass substrate at a temperature of usually 200 to 400°C, preferably 250 to 350°C to cause the amide imidization reaction, and the polyimide can be obtained film. From the viewpoint of sufficiently performing imidization, the heating temperature is 200° C. or higher, and from the viewpoint of thermal stability of the resulting polyimide film, the heating temperature is preferably 400° C. or lower.

Although the imidization reaction is desirably carried out in a vacuum or an inert gas, when the imidization temperature has to be too high, even if the imidization reaction is carried out in air.

Next, the thermal imidization method will be described in detail. First, the polyamic acid solution having the repeating unit represented by the above formula (2) of the present invention obtained by using the above method is added with the same solvent as in the polymerization and made into a moderate solution viscosity that is easy to stir, followed by stirring ,One While dropping the anhydride of the organic acid and the dehydration ring-closing agent (chemical amide imidization agent) composed of tertiary amine as an alkaline catalyst, the solution is stirred at a temperature of 0-100°C, preferably 10-50°C 1~72 hours, can complete the chemical imidization. Examples of organic acid anhydrides that can be used at this time include acetic anhydride and propionic anhydride. Among these acid anhydrides, acetic anhydride is preferably used from the viewpoint of handling of the reagent and easy separation. Meanwhile, as for the basic catalyst, pyridine, triethylamine, quinoline and the like can be used. Among these basic catalysts, it is preferable to use pyridine from the viewpoints of treatment of the reagent and easy separation. The content of the organic acid anhydride in the chemical amide imidization agent is in the range of 1 to 10 times the molar amount of the theoretical dehydration amount of the polyamic acid, preferably 2 to 10 times the mole. At the same time, the content of the basic catalyst is in the range of 0.1 to 5 times the molar amount relative to the organic acid anhydride, preferably in the range of 1 to 5 times the molar amount.

The reaction solution obtained by the above-mentioned chemical imidization method is mixed with alkali or unreacted chemical imidization agent, organic acid and other by-products (hereinafter referred to as impurities), so in order to remove these It is better to separate and refine the polyimide. It can be refined by a known method. For example, as far as the simplest method is concerned, the following method can be applied: after the imidized reaction solution is dropped into a large amount of lean solution, and the polyimide is precipitated, the polyimide powder is It was recovered and washed repeatedly until impurities were removed, and then dried under reduced pressure to obtain polyimide powder. At this time, as far as the solvent can be used, as long as it can precipitate polyimide and can efficiently remove impurities, and is easy to dry, it is not particularly limited, but for example, water or methanol can be applied , Ethanol, isopropanol and other alcoholic solvents can also be mixed and used. Once the polyimide solution is dropped into the lean solution to precipitate the polyimide, the solid content of the polyimide solution is too high, the precipitated polyimide becomes pellets, and some impurities remain in the coarse particles, or it takes a long time Only when the obtained polyimide powder is dissolved in the solvent again. On the other hand, once the concentration of the polyimide solution is too dilute, a large amount of lean solvent becomes required, which increases the environmental load or the manufacturing cost caused by the treatment of a large amount of waste solvent. Therefore, the concentration of the polyimide solution when dropped into the lean solution is 20% by weight or less, preferably 10% by weight or less. The amount of poor solvent used at this time is relative to polyimide The amount of the solution is more than 1 times by weight, more preferably 1.5 to 10 times by weight. The obtained polyimide powder is recovered, and residual solvent is removed using vacuum drying or hot air drying. As long as the temperature does not deteriorate the polyimide, the drying temperature and time are not limited. Preferably, the temperature is 30 to 150°C.

In the case where the polyimide powder having the repeating unit represented by the above formula (3) thus obtained is made into a polyimide film, it is necessary to convert the one having the repeating unit represented by the above formula (3) Polyimide powder is temporarily dissolved in a solvent and made into a polyimide solution. As far as the usable solvent is concerned, as long as it can properly dissolve the polyimide powder in accordance with the usage and processing conditions, specific examples include N,N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide-based solvents, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, Ester-based solvents such as ε-caprolactone, α-methyl-γ-butyrolactone, butyl acetate, ethyl acetate, isobutyl acetate, etc., carbonic acid-based solvents such as ethyl carbonate and propyl carbonate, Diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether and other glycol-based solvents, phenol, m-cresol, p-cresol, o-cresol, 3-chlorophenol, 4-chlorophenol Phenol solvents such as cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone and other ketone solvents, tetrahydrofuran, 1,4-dioxane, In addition to ether systems such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dibutyl ether, acetophenone, 1,3-dimethyl-2-imidazolidinone, cyclobutane, dimethyl Glyphosate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, ethyl cellosolve acetate, butyl Cellulose acetate, butanol, ethanol, xylene, toluene, chlorobenzene, turpentine, mineral spirits, naphtha-based solvents and other general-purpose solvents, these solvents can be used alone, or can be used in combination of two or more. The method of dissolving the polyimide powder can be in air or in an inert gas, using a temperature range from room temperature to the boiling point of the solvent or less, to dissolve the polyimide powder to form a polyimide solution.

For example, casting the polyimide solution thus obtained on a glass substrate, Then, by heating in a vacuum or an inert gas such as nitrogen, a polyimide film can be obtained. For example, in general, a film of polyamic acid can be obtained by drying in an oven at 200 to 400°C, preferably 250 to 350°C. Although the production of the polyamic acid film is expected to be carried out in vacuum or inert gas, when the temperature has to be too high, it is no problem to carry out the amide imidization reaction in air.

The molecular weight of the polyimide having the repeating unit represented by the above formula (3) obtained by the above method is measured by a measurement method described later, and the molecular weight measured by weight average molecular weight is preferably 10,000 The above is more preferably 20,000 or more, and particularly preferably 40,000 or more, and at the same time, preferably 600,000 or less, more preferably 500,000 or less, and particularly preferably 300,000 or less. Once the molecular weight of the polyimide is 10,000 or more, it can be molded, and at the same time, it is easy to maintain good mechanical properties. Furthermore, once the molecular weight of the polyimide is 300,000 or less, the molecular weight during synthesis can be easily controlled, and at the same time, a solution with an appropriate viscosity is often obtained and therefore easy to handle. In addition, for the molecular weight of the polyamic acid, the viscosity of the polyamic acid solution can be used as a reference.

The dielectric constant of the polyimide having the repeating unit represented by the above formula (3) of the present invention obtained by the above method is usually 3.0 or less, preferably 2.9 or less, so it can be suitably used as an interlayer insulating film . At the same time, because of the high value of the 400nm light transmittance (T ₄₀₀ ) of the polyimide film, the transparency is excellent, and even worse, because of the tetrahydrofuran, cyclopentanone, N,N-dimethylformamide , N,N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone and other solvents have excellent solubility, so it can be used as a low dielectric transparency polyimide and suitable for Used as optical materials and electronic materials.

[Example]

The embodiments of the present invention are shown below, but the present invention is not limited to these embodiments.

[1] NMR measurement

^{The 1} H-NMR and ¹³ C-NMR systems use tetramethylsilane as an internal standard and heavy DMSO (dimethyl sulfoxide) as a solvent, which is recorded by a JEOL-ESC400 spectrometer.

[2] LC-MS determination

LC-MS is based on the following measurement conditions for separation, mass analysis, and identification of the target.

‧Installation: "Xevo G2 Q-Tof" made by Waters

‧Column: L-Column2 ODS (2μm, 2.1mm ψ×100mm)

‧Column temperature: 40℃

‧Detection wavelength: UV 220~500nm

‧Mobile phase: Liquid A = 0.1% formic acid water, Liquid B = methanol

‧Mobile phase flow: 0.3ml/min

‧Gradient of mobile phase: Liquid B concentration: 80% (0 minutes)→80% (after 10 minutes)→100% (after 15 minutes)

‧Test method: Q-Tof

‧Ionization method: APCI(-) method

‧Ion source: temperature 150℃

‧Sampling cone: voltage 60V, airflow 50L/h

‧Desolvated gas: temperature 500℃, air flow 1000L/h

[3] HPLC purity

The area percentage value at the time of HPLC measurement using the following measurement conditions was taken as the purity of each compound.

Liquid chromatography determination conditions:

‧Installation: L-2130 manufactured by Hitachi, Ltd.

‧Tube: ZORBAX CN (5 μm , 4.5mm ψ×250mm)

‧Mobile phase: hexane/THF, flow rate: 1.0ml/min

‧Column temperature: 40℃, detection wavelength: UV 254nm

[4] Weight average molecular weight of polyamide

The weight average molecular weight was measured using the following measurement conditions. (Converted to polystyrene)

Device: HLC-8320GPC manufactured by Tosoh Corporation

Column: TSK-GEL Super AWM-H (6.0mm I.D.×15cm)

Mobile phase: N,N-dimethylformamide, flow rate: 1.0ml/min

Column temperature: 40℃

[5] Determination of melting point

A differential scanning calorimeter ("EXSTAR DSC 220" manufactured by Seiko Instruments Nanotechnology Co., Ltd.) was used and measured at a heating rate of 10°C/min.

[6] Determination of glass transition temperature (Tg)

A differential scanning calorimeter ("EXSTAR DSC 220" manufactured by Seiko Instruments Nanotechnology Co., Ltd.) was used and the temperature was measured at a heating rate of 20°C/min.

[7] Determination of 5% weight loss temperature (T _d ⁵ )

A thermal analysis device (Thermo Plus Evo II TG-DTA8121/S manufactured by Rigaku Corporation) was used and measured at a temperature increase rate of 10°C/min.

[8] Determination of cutoff wavelength

Using a spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation), the transmittance of the polyimide film at 200 to 800 nm was measured. The wavelength with a transmittance of 0.5% or less is used as the cutoff wavelength. The shorter the cutoff wavelength, the better the transparency of the polyimide film.

[9] Determination of light transmittance (T ₄₀₀ )

The 400 nm transmittance of the polyimide film was measured using a spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation). The higher the penetration rate, the better the transparency of the polyimide film.

[10] Dielectric rate (ε)

Use Abbe Refractometer ("Multi-wavelength Abbe Refractometer DR-M2" manufactured by ATAGO), and use the refractive index (wavelength: parallel to the direction (n _in ) and vertical direction (n _out ) of the polyimide film 589 nm), and the average refractive index (n _av ) of the polyimide film was determined by the following formula.

n _av = (2n _in +n _out )/3

Based on this average refractive index (n _av ), the dielectric constant (ε) of the polyimide film in 1 MHz was calculated by the following formula.

ε=1.1 xn _av ²

[11] Solvent solubility

Put 20 mg of the obtained polyimide film or polyimide powder into 1 mL of N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and tetrahydrofuran (THF ), m-cresol (m-Cr), the solubility test. The solvent solubility was evaluated in the following arrangement.

○: Dissolve at room temperature.

△: It dissolves once heated, and does not precipitate even after cooling to room temperature.

╳: Insoluble.

1. Production of tetracarboxylic dianhydride having cyclic hydrocarbon skeleton and ester group represented by the above formula (1)

<Example 1>

(In the tetracarboxylic dianhydride represented by the above formula (1), the tetracarboxylic dianhydride represented by the following formula (1-A) (in the above formula (1), m=n=1, x=5, R ₁ and R _{2 (} methyl) production examples)

In a 1L four-necked flask equipped with a thermometer, a dropping funnel and a stirrer, 83.0g (394.2mmol) of trimellitic anhydride chloride and 100.0g of ethylene glycol dimethyl ether were placed, and after stirring and complete dissolution, cooling was started. Mix a mixture of 1,1-bis(4-hydroxy-3-methylphenyl)cyclododecane 50.0g (131.4mmol), ethylene glycol dimethyl ether 150.0g and pyridine 31.2g (394.2mmol) in It took 1 hour to drop to the aforementioned flask at 0°C to 9°C. After that, it was kept at 0°C to 5°C and stirred for 30 minutes. After that, the temperature was raised to 55°C and the temperature was maintained at 55°C to 60°C and stirred for 4 hours, followed by stirring at 65°C to 70°C for two hours. Stop heating and place 228.8 g of ethylene glycol dimethyl ether, filter at 25°C to 26°C and wash 3 times with ethylene glycol dimethyl ether to obtain crude crystals. By adding acetonitrile as a crude crystal and repeating the step of heating and refluxing for one hour twice, 57.08 g of white crystals were obtained (yield 59.6%, purity 99.2%). From the ¹ H-NMR spectrum shown in FIG. 1, the ¹³ C-NMR spectrum shown in FIG. 2 and the mass spectrum shown in FIG. 3, it was confirmed that the obtained product was the tetracarboxylic acid represented by the above formula (1-A) Dianhydride. Hereinafter, ¹ H-NMR and ¹³ C-NMR of the obtained tetracarboxylic dianhydride represented by the above formula (1-A) will be described in detail.

The ¹ H-NMR (DMSO-d ₆ ) chart of the obtained tetracarboxylic dianhydride represented by the above formula (1-A) is shown in FIG. 1. Here, the peak system from 8.27 to 8.66 ppm is derived from the hydrogen atom on the benzene ring of trimellitic acid, and the peak system from 7.05 to 7.20 ppm is 1,1-bis(4-hydroxy-3-methylphenyl) ring. The hydrogen atoms of the benzene ring in the dioxane structure, the hydrogen atoms of the methyl group of 2.17 ppm, and the peaks of 0.91 to 2.05 ppm belong to the hydrogen atoms of the cyclododecane structure. In addition, the peak observed at 2.5 ppm is DMSO as a solvent, and the peak observed at 3.3 ppm is derived from water contained in DMSO.

The ¹³ C-NMR chart is shown in FIG. 2. Here, 162.3 to 162.5 ppm and 128.7 to 136.9 ppm are carbon atoms derived from trimellitic anhydride structure, and 121.3 ppm and 125.7 to 126.2 ppm are derived from 1,1-bis(4-hydroxy-3-methylphenyl) The carbon atom of the benzene ring in the cyclododecane structure, the peak of 47.5 ppm is the carbon atom of the methyl group, and 16.0~32.4 ppm belongs to the carbon atom of the cyclododecane structure. In addition, the peaks observed at 39.1 to 39.6 ppm are derived from DMSO as a solvent.

The mass spectrum value and melting point of the obtained tetracarboxylic dianhydride represented by the above formula (1-A) are as follows The following.

Mass spectrum value (M- ^. ): 728.26

Melting point (DSC): 182°C

2. Production of a polyamic acid having a repeating unit represented by the above formula (2) and a polyimide having a repeating unit represented by the above formula (3)

<Example 2>

(In the polyamic acid represented by the above formula (2), the tetracarboxylic dianhydride represented by the above formula (1-A) and 4,4'-diaminodiphenyl ether (4,4'-ODA) Polyamide acid obtained by reaction (manufacture of polyamic acid having a repeating unit represented by the following formula (2-A))

At room temperature, 4.0 g (5.49 mmol) of the tetracarboxylic dianhydride represented by the above formula (1-A) and 4,4′-ODA 1.1 g (5.49 mmol) obtained in Example 1 were dissolved in N, 45.9 g of N-dimethylacetamide was reacted at room temperature for 27 hours to synthesize the N,N-dimethylacetamide solution of the polyamic acid represented by the above formula (2-A). The weight average molecular weight (Mw) of polyamide is 409,266.

<Example 3>

(In the polyimide represented by the above formula (3), by chemical imidization of the polyamic acid having the repeating unit represented by the above formula (2-A), the following formula (3 -A) Polyimide of the repeating unit shown.)

[Chem 13]

By adding 73.5 g of N,N-dimethylacetamide, 21.1 g of acetic anhydride, and 8.2 g of pyridine to the repeating unit represented by the above formula (2-A) obtained in the same manner as in Example 2 73.5 g of N,N-dimethylacetamide solution (solute concentration 26.0% by weight) of polyamic acid and stirring at room temperature for 24 hours to synthesize the repeating unit represented by the above formula (3-A) A solution of polyimide in N,N-dimethylacetamide (solute concentration 13.0% by weight).

The N,N-dimethylacetamide solution of the obtained polyimide having the repeating unit represented by the above formula (3-A) is further diluted with an N,N-dimethylacetamide solution to make it It became a 9% by weight solution, and by dropping it into 600 g of methanol, polyimide having a repeating unit represented by the above formula (3-A) was precipitated. The precipitated polyimide was filtered, washed with methanol, and then dried to obtain 17.8 g of pale yellow polyimide powder.

By adding 2.5 g of the obtained polyimide powder to 22.8 g of N-methyl-2-pyrrolidone and stirring until uniform, N of polyimide having the repeating unit represented by the above formula (3-A) is obtained -Methyl-2-pyrrolidone solution. After coating this solution on a glass substrate, it was heated at 150°C for one hour and then at 250°C for one hour to obtain a thin film of a polyimide having a repeating unit represented by the above formula (3-A). The thickness of the thin film is about 20 μm. Measurement results of glass transition temperature (Tg), 5% weight loss temperature (T _d ⁵ ), cutoff wavelength, light transmittance at 400 nm (T ₄₀₀ ) and dielectric permittivity (ε) of the obtained polyimide film Shown in Table 1. At the same time, the solubility in various solvents is shown in Table 2.

<Example 4>

(In the polyamic acid represented by the above formula (2), the tetracarboxylic dianhydride represented by the above formula (1-A) and 9,9-bis (Production of polyamic acid (polyamide having a repeating unit represented by the following formula (2-B)) obtained by reacting (4-aminophenyl) fluorene (FDA))

At room temperature, 7.0 g (9.61 mmol) of the tetracarboxylic dianhydride represented by the above formula (1-A) obtained in Example 1 and 3.4 g of 9,9-bis(4-aminophenyl)fluorene ( 9.61 mmol) was dissolved in 25.6 g of N,N-dimethylacetamide, and then reacted at room temperature for 24 hours to synthesize N,N of a polyamic acid having a repeating unit represented by the above formula (2-B) -Dimethyl acetamide solution. The weight average molecular weight (Mw) of polyamide is 50,954.

<Example 5>

(In the polyimide represented by the above formula (3), by chemical imidization of the polyamic acid having the repeating unit represented by the above formula (2-B), the following formula (3 -B) Polyimide of the repeating unit shown.)

By adding 43.0 g of N,N-dimethylacetamide, 9.5 g of acetic anhydride and 3.7 g of pyridine to the polyamic acid having the repeating unit represented by the above formula (2-B) obtained in Example 4 N,N-dimethylacetamide solution (solute concentration 28.8% by weight) 34.8g, followed by stirring at room temperature for 24 hours A solution of polyimide having a repeating unit represented by the above formula (3-B) in N,N-dimethylacetamide solution (solute concentration 13.0% by weight).

The N,N-dimethylacetamide solution of the obtained polyimide having the repeating unit represented by the above formula (3-B) was diluted with N,N-dimethylacetamide to become 10% by weight The solution was then diluted with N-methyl-2-pyrrolidone to make it a 9% by weight solution, which was precipitated by dropping it into 350 g of methanol to precipitate a repeat having the above formula (3-B) Unit of polyimide. The precipitated polyimide was filtered and washed with methanol, and then dried to obtain 8.6 g of pale yellow polyimide powder.

By adding 4.0 g of the obtained polyimide powder to 16.0 g of N,N-dimethylacetamide and stirring until uniform, a polyimide having a repeating unit represented by the above formula (3-B) is obtained Amine solution in N,N-dimethylacetamide. After coating this solution on a glass plate, it was heated at 150°C for one hour and then at 250°C for one hour to obtain a thin film of a polyimide having a repeating unit represented by the above formula (3-B). The thickness of the thin film is about 24 μm. Table 1 shows the measurement results of the glass transition temperature (Tg), cutoff wavelength, light transmittance (T ₄₀₀ ) and dielectric constant (ε) of the obtained polyimide thin film at 400 nm. At the same time, the solubility in various solvents is shown in Table 2.

<Example 6>

(In the polyamic acid represented by the above formula (2), the tetracarboxylic dianhydride represented by the above formula (1-A) and 3,3'-diaminodiphenyl sulfone (3,3'-DDS ) Production of Polyamide Acid (Polyamide Acid with Repeating Unit Represented by the Following Formula (2-C))

At room temperature, 4.0 g (5.49 mmol) of the tetracarboxylic dianhydride represented by the above formula (1-A) obtained in Example 1 and 1.4 g (5.48 mmol) of 3,3′-diaminodiphenylbenzene ) Dissolved in 13.3g of N,N-dimethylacetamide, followed by a reaction at room temperature for 24.5 hours to synthesize N,N-dimethylethyl of the polyamic acid represented by the above formula (2-C) Acetylamine solution. The weight average molecular weight (Mw) of polyamide is 54,896.

<Example 7>

(In the polyimide represented by the above formula (3), by chemical imidization of the polyamic acid having a repeating unit represented by the above formula (2-C), the following formula (3 -C) Polyimide of the repeating unit shown)

By adding 8.2 g of N,N-dimethylacetamide, 5.6 g of acetic anhydride, and 2.2 g of pyridine, the polyamide obtained in Example 6 having the repeating unit represented by the above formula (2-C) 18.6 g of N,N-dimethylacetamide solution (solute concentration 28.8% by weight), and stirred at room temperature for 25 hours to obtain a polyimide having a repeating unit represented by the above formula (3-C) Of N,N-dimethylacetamide solution (solute concentration 20.0% by weight).

By dropping the N,N-dimethylacetamide solution of the polyimide obtained as the repeating unit represented by the above formula (3-C) into 200 g of methanol, the above formula (3-C) is precipitated Polyimide with repeating units shown. The precipitated polyimide was filtered and washed with methanol, and then dried to obtain 5.0 g of pale yellow polyimide powder.

By adding 4.0 g of the obtained polyimide powder to 16.0 g of N,N-dimethylacetamide and stirring until uniform, a polyimide having a repeating unit represented by the above formula (3-C) is obtained Amine solution in N,N-dimethylacetamide. After the obtained solution was applied to a glass plate, it was heated at 150°C for one hour and then at 250°C for one hour to obtain a thin film of polyimide having a repeating unit represented by the above formula (3-C). The thickness of the thin film is about 20 μm. Table 1 shows the measurement results of the glass transition temperature (Tg), cutoff wavelength, light transmittance (T ₄₀₀ ) of 400 nm, and dielectric permittivity (ε) of the obtained polyimide film. At the same time, the solubility in various solvents is shown in Table 2.

<Example 8>

(In the polyamic acid represented by the above formula (2), the tetracarboxylic dianhydride represented by the above formula (1-A) and 2,2'bis(trifluoromethyl)-4,4'-diamine Polyacrylic acid (polyamide having a repeating unit represented by the following formula (2-D)) obtained by the reaction of a biphenyl (alias 2,2'bis(trifluoromethyl)-benzidine) (TFMB) Acid))

At room temperature, 4.0 g (5.49 mmol) of the tetracarboxylic dianhydride represented by the above formula (1-A) obtained in Example 1 and 2,2'bis(trifluoromethyl)-4,4'- Diaminobiphenyl (alias 2,2'bis(trifluoromethyl)-benzidine) 1.76g (5.49mmol) was dissolved in N.N-dimethylacetamide 14.24g, then reacted at room temperature 24 The N,N-dimethylacetamide solution of polyamic acid having the repeating unit represented by the above formula (2-D) is synthesized in hours. The weight average molecular weight (Mw) of polyamide is 136,263.

<Example 9>

(In the polyimide represented by the above formula (3), by chemical imidization of the polyamic acid having the repeating unit represented by the above formula (2-D), the following formula (3 -D) Polyimide of the repeating unit shown.)

[Chem 19]

By adding 8.81 g of N,N-dimethylacetamide, 5.6 g of acetic anhydride, and 2.2 g of pyridine to the polyamic acid having the repeating unit represented by the above formula (2-D) obtained in Example 8 N,N-dimethylacetamide solution (solute concentration 28.8% by weight) 20.0 g, followed by stirring at room temperature for 24 hours to obtain a polyimide having a repeating unit represented by the above formula (3-D) N,N-dimethylacetamide solution (solute concentration 20.0% by weight).

By dropping the N,N-dimethylacetamide solution of the polyimide of the repeating unit represented by the above formula (3-D) into 200 g of methanol, the compound represented by the above formula (3-D) is precipitated The repeating unit of polyimide. The precipitated polyimide was filtered and washed with methanol, and then dried to obtain 5.6 g of pale yellow polyimide powder.

By adding 5.0 g of the obtained polyimide powder to 20.0 g of N,N-dimethylacetamide and stirring until uniform, a polyimide having a repeating unit represented by the above formula (3-D) is obtained Amine solution in N,N-dimethylacetamide. After coating the obtained solution on a glass plate, it was heated at 150° C. for one hour and then at 250° C. for one hour to obtain a thin film of polyimide having a repeating unit represented by the above formula (3-D). The thickness of the thin film is about 28 μm. Table 1 shows the measurement results of the glass transition temperature (Tg), cutoff wavelength, light transmittance (T ₄₀₀ ) of 400 nm, and dielectric permittivity (ε) of the obtained polyimide film. At the same time, the solubility in various solvents is shown in Table 2.

<Comparative Example 1>

(Tetracarboxylic acid dianhydride having a fluorene structure and an ester group (the following formula (8-A))

(A production example of polyimide having a repeating unit represented by the following formula (8-C) obtained by reaction with 4,4'-diaminodiphenyl ether (4,4'-ODA))

According to the description in Japanese Patent Laid-Open No. 2007-91701, a polyimide having a repeating unit represented by the above formula (8-C) (polyamide having a fluorene structure and an ester group) is obtained Amine) film. At the same time, the weight average molecular weight (Mw) of the polyamic acid before becoming polyimide was 150,356, and the film thickness of the obtained film was 22 μm. Measurement results of glass transition temperature (Tg), 5% weight loss temperature (T _d ⁵ ), cutoff wavelength, light transmittance at 400 nm (T ₄₀₀ ) and dielectric permittivity (ε) of the obtained polyimide film Shown in Table 1. At the same time, the solubility in various solvents is shown in Table 2.

Claims (1)

A tetracarboxylic dianhydride characterized by the following formula (1):

(In the formula, x represents an integer of 1 to 11, and R ₁ and R ₂ each independently represent an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, a cycloalkyl group having 4 to 16 carbon atoms, or a carbon number 6 to 12 aromatic groups; when R ₁ and/or R ₂ are present in plural, they may be the same or different; m and n each independently represent an integer of 0 or 1 to 4).

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