KR102335654B1 - Tetracarboxylic dianhydride, polyamic acid and polyimide - Google Patents

Abstract

The polyamic acid and polyimide which can be obtained from the tetracarboxylic dianhydride represented by Formula (1), its manufacturing method, and this tetracarboxylic dianhydride are provided.

Description

Tetracarboxylic dianhydride, polyamic acid and polyimide

The present invention relates to a novel tetracarboxylic dianhydride having a fluorenyl group, an ether group and an ester group useful as a raw material for polyimide resins and the like, and a polyamic acid and polyimide obtained from the tetracarboxylic dianhydride.

A resin material having a high refractive index has high workability compared to conventional glass materials, and the like. , substrates, various optical filters, prisms, optical elements for communication, etc. have been widely applied, and as resins exhibiting these high refractive indexes, for example, polyester, polycarbonate, polyimide, etc. have been proposed. Among these, polyimide is known as a resin excellent in heat resistance, and a polyimide having a high refractive index and excellent heat resistance is required in the field where heat resistance is particularly required among the above applications.

However, most polyimides with high heat resistance are insoluble in organic solvents, and it is usually not easy to mold the polyimide itself. Therefore, it is necessary for a polyimide to form a film|membrane etc. with the polyamic-acid solution of a precursor, and to obtain a polyimide film by heat-dehydrating ring closure (imidization) at high temperature like 250-350 degreeC. However, the method of obtaining a polyimide film by imidation after shape|molding a film|membrane etc. with the solution of a polyamic acid is thermal stress generated in the process of cooling from imidization temperature (250-350 degreeC) to room temperature. , sometimes causing problems such as curling, film peeling, cracking, etc., so there is a problem that a uniform polyimide film cannot be obtained, and at the same time, a high-temperature furnace of 300 ° C. or higher is required for imidization, which increases the manufacturing cost. There were also shortcomings.

Therefore, as a polyimide which is excellent in solvent solubility and expresses a high refractive index, the polyimide obtained from the aromatic diamine compound which has a naphthalene skeleton, for example is proposed [Unexamined-Japanese-Patent No. 2010-070513 (patent document 1). ]. The polyimide described in that document is soluble in a solvent and has a high refractive index with a refractive index of about 1.63. However, from the demand for higher refractive index for resin materials these days, a new improvement of the refractive index has been demanded.

Japanese Patent Laid-Open No. 2010-070513

An object of the present invention is to provide a polyimide which is excellent in solvent solubility and exhibits a high refractive index.

As a result of the inventors examining various structures of tetracarboxylic dianhydride and diamine which are polyimide raw materials in order to solve the said subject, tetracarboxylic dianhydride which has fluorene structure represented by following formula (1) It was found that the polyimide prepared using the excellent solvent solubility and high refractive index. Specifically, the present invention includes the following.

〔One〕

Equation (1) below:

[Formula 1]

Tetracarboxylic dianhydride represented by

〔2〕

Equation (2) below:

[Formula 2]

(wherein Z represents a diamine residue)

A polyamic acid having a repeating unit represented by

[3]

Equation (3) below:

[Formula 3]

(wherein Z represents a diamine residue)

A polyimide having a repeating unit represented by

〔4〕

Trimellitic anhydride halide and the formula (4):

[Formula 4]

The method for producing tetracarboxylic dianhydride according to [1], wherein the bisphenol represented by is reacted.

The polyimide manufactured using tetracarboxylic dianhydride which has fluorene skeleton of this invention is excellent in solvent solubility, and has the characteristic of high refractive index. Furthermore, in that it has excellent toughness despite having a rigid structure such as a fluorene skeleton, spectacle lenses, lenses such as cameras, lenses for optical disks, fθ lenses, optical system elements of image display media, In addition to use in the field of optical systems such as optical films, films, various optical filters, prisms, and optical elements for communication, electronic materials such as flexible printed wiring circuit boards, semiconductor element protective films, and interlayer insulating films of integrated circuits, liquid crystal displays, electronics It can be suitably used also for uses, such as a flexible substrate replacing the glass substrate normally used for paper, a solar cell, etc.

^{1 : is 1} H-NMR spectrum of tetracarboxylic dianhydride represented by Formula (1).
^{It is 13} C-NMR spectrum of tetracarboxylic dianhydride represented by Formula (1).
It is a mass spectrometry chart of tetracarboxylic dianhydride represented by Formula (1).

<The manufacturing method of tetracarboxylic dianhydride represented by Formula (1)>

As a method of obtaining tetracarboxylic dianhydride represented by said Formula (1), a well-known method is applicable suitably. For example, in the presence of a deoxidizing agent (base), the compound represented by the formula (4) (9,9-bis(4-(4-hydroxyphenyloxy)phenyl)fluorene, hereinafter abbreviated as BPOPF ) and an acid halide of trimellitic anhydride (acid halide method), a method by direct dehydration reaction between BPOPF and trimellitic anhydride, deacetic acid reaction of a diacetate of BPOPF and trimellitic anhydride at high temperature method, a method of dehydration condensation of BPOPF and trimellitic anhydride using a dehydrating agent such as dicyclohexylcarbodiimide, a method of activating trimellitic anhydride using a tosyl chloride/N,N-dimethylformamide/pyridine mixture The method of esterifying BPOPF is mentioned. Among them, the acid halide method is preferable because trimellitic acid halide as a raw material can be obtained inexpensively. Hereinafter, the acid halide method is described in detail.

Specifically, the acid halide method is a reaction in which BPOPF and an acid halide of trimellitic anhydride represented by the following formula (5) are reacted in the presence of a deoxidizing agent to obtain tetracarboxylic dianhydride represented by the formula (1). (Hereinafter, this reaction may be called an esterification reaction).

A commercial item may be used for BPOPF used as a raw material, and it can also manufacture by a well-known method (For example, International Publication No. 2006/052001, Unexamined-Japanese-Patent No. 2015-182970). Specifically, it can be obtained by reacting fluorenone with p-phenoxyphenol in the presence of an acid.

The acid halide of trimellitic anhydride used in the esterification reaction has the following formula (5):

[Formula 5]

(wherein Y represents a halogen atom)

It has a structure represented by Among these acid halides of trimellitic anhydride, since the acid chloride of trimellitic anhydride can be obtained at low cost, Y is preferably a chlorine atom.

The usage-amount of the acid halide of the trimellitic acid anhydride represented by the said Formula (5) used for esterification reaction is 2-4 times mole with respect to 1 mol of BPOPF normally, Preferably it is 2-3 times mole. A sufficient reaction rate can be obtained by making the usage-amount of the acid halide of trimellitic acid anhydride 2 times mole or more, and the acid halide of unreacted trimellitic acid anhydride represented by said Formula (5) is reduced by making the usage-amount 4 times mole or less. It is possible to make it, and as a result, it becomes possible to improve the purity of the tetracarboxylic dianhydride represented by said Formula (1) obtained.

As the deoxidizer used in the esterification reaction, for example, organic tertiary amines such as pyridine, triethylamine, N,N-dimethylaniline, epoxies such as propylene oxide and allyl glycidyl ether, potassium carbonate, sodium hydroxide Inorganic bases, such as these are mentioned. These deoxidizers may be used alone or in combination of two or more as needed. Among these deoxidizers, pyridine is preferably used because it is inexpensive and can be easily separated and removed after the reaction. The usage-amount of a deoxidizer is 2-4 times mole normally with respect to 1 mol of BPOPF, Preferably it is 2-3 times mole. By making the usage-amount of a deoxidizer into 2 times mole or more, a reaction rate improves, and it becomes possible to suppress generation|occurrence|production of an impurity by setting it as 4 times mole or less.

When carrying out the esterification reaction, an organic solvent can be used as needed. As the usable organic solvent, for example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers such as 1,2-dimethoxyethane, tetrahydrofuran, and cyclopentyl methyl ether, benzene, toluene, xyl Aromatic hydrocarbons such as ren, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, nitriles such as acetonitrile, propanonitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, and benzonitrile is exemplified From the viewpoint of availability and handleability, preferably ethers, aromatic hydrocarbons, and nitriles, these organic solvents may be used alone or as a mixture of two or more as needed. When using these solvents, the usage-amount is 1-30 weight times with respect to 1 weight times of BPOPF normally, Preferably it is 1-5 weight times.

The esterification reaction is usually carried out at -10°C to 110°C, preferably at -5°C to 80°C, more preferably at 20°C to 70°C. By setting the reaction temperature to 110°C or lower, reduction of by-products becomes possible, and by setting the reaction temperature to -10°C or higher, a sufficient reaction rate can be obtained.

As the esterification reaction, for example, a solution in which the acid halide of trimellitic anhydride represented by the above formula (5) and a solvent are mixed with the solution, while the solution is stirred, a solution obtained by mixing separately prepared BPOPF and a deoxidizing agent in a solvent; After adding intermittently or continuously so as to reach the above temperature range, there is a method in which the reaction is further continued in the above temperature range. In addition, to a solution in which the acid halide of trimellitic anhydride represented by the formula (5) and BPOPF are mixed in a solvent, the deoxidizer is added as it is or after mixing it with the solvent, intermittently or continuously so as to reach the above temperature range, and addition After that, a method of further continuing the reaction in the above-described temperature range may be used.

After completion of the esterification reaction, crystals are precipitated by cooling the reaction mass to 15°C to 35°C, and the crystals obtained by filtration separation of the precipitated crystals are further washed with a solvent usable in the above-mentioned reaction, the formula ( The tetracarboxylic dianhydride represented by 1) can be obtained (Hereinafter, this process may be called a crystallization process). With respect to the obtained tetracarboxylic dianhydride represented by said Formula (1), general refinement|purification, such as an adsorption process and re-crystallization, can also be performed as needed.

In addition, after completion of the esterification reaction, before performing the above-mentioned crystallization step, if necessary, water and an organic solvent separated from water are added to the reaction mass, followed by stirring and separating the water layer (hereinafter, washing with water) process), the tetracarboxylic dianhydride represented by the formula (1) is extracted into the organic solvent layer, an excess deoxidizer and a hydrolyzate of the acid halide of trimellitic anhydride, and a deoxidizer After distributing and removing the halogen salt of the water layer, a ring-opened product (hydrolyzed product of tetracarboxylic dianhydride represented by the above formula (1)) produced by the water washing step is further subjected to a ring closure reaction in the presence of an organic solvent and acetic anhydride, , you may perform the process set as tetracarboxylic dianhydride represented by said Formula (1) again.

The tetracarboxylic dianhydride obtained by the above method and represented by the formula (1) may be used not only as a raw material for polyimide, but also as a raw material for a resin such as polyester, an additive, an epoxy resin, or a curing agent for a polyurethane resin. . Moreover, the purity of the tetracarboxylic dianhydride represented by the said Formula (1) is the point which it is easy to improve the polymerization degree of the polyamic acid represented by the said Formula (2), or the polyimide represented by the said Formula (3), The method mentioned later HPLC purity measured by , preferably 95% or more, particularly preferably 99% or more.

<The polyamic acid which has a repeating unit represented by said Formula (2), and its manufacturing method>

The polyamic acid (Hereinafter, it may call the polyamic acid of this invention) which has a repeating unit represented by said Formula (2) is demonstrated in detail.

The polyamic acid of this invention has a repeating unit represented by the said Formula (2), The diamine residue represented by Z in the said Formula (2) is tetracarboxylic dianhydride represented by the said Formula (1), and obtained when reacted a diamine, shows the structural parts other than the amino groups of the diamine (-NH _2).

It is preferable that it is 10,000-700,000 with the weight average molecular weight obtained by the measuring method mentioned later, and, as for the molecular weight of the polyamic acid of this invention, it is more preferable that it is 20,000-600,000. If the molecular weight of a polyamic acid is 10,000 or more, it is easy to maintain a shape|molding and favorable mechanical property. Moreover, when the molecular weight of a polyamic acid is 700,000 or less, when synthesize|combining, it is easy to control molecular weight, and it is easy to obtain the solution of an appropriate viscosity, and handling is easy in many cases. In addition, the molecular weight of a polyamic acid can be made into the reference|standard of the viscosity of a polyamic-acid solution.

After melt|dissolving the diamine mentioned later in the polymerization solvent mentioned later, for example, the polyamic acid of this invention adds the powder of tetracarboxylic dianhydride represented by said Formula (1) at 10-20 degreeC normally , 10-100 degreeC, Preferably it can obtain as a polyamic-acid solution (it may call a polyamic-acid solution hereafter) by stirring at 10-30 degreeC.

As the diamines usable in the present invention, general aromatic diamines, aliphatic diamines, alicyclic diamines, etc. used for the production of polyimide can be used. As such diamines, for example, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'- Diaminodiphenyl ether (alias 4,4'-oxydianiline), 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4' -diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (alias 2,2 '-bis(trifluoromethyl)benzidine), 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone , 4,4'-bis(4-aminophenyl)sulfide, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 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-dimethylpropane, 1 ,2-bis[2-(4-aminophenoxy)ethoxy]ethane, 9,9-bis(4-aminophenyl)fluorene, 5(6)-amino-1-(4-aminomethyl)-1 ,3,3-trimethylindane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane , bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoro Ropropane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 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)tetramethyldisiloxane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4'-methylenebis(4-cyclohexylamine) , trans-1,4-cyclohexanediamine, bicyclo[2.2.1]heptanebis(meth tylamine), tricyclo[3.3.1.13,7]decane-1,3-diamine (alias adamantane-1,3-diamine), 4-aminobenzoic acid-4-aminophenyl ester, 2-(4-amino Phenyl)aminobenzoxazole, 9,9-bis[4-(4-aminophenoxy)phenyl]fluorene, 2,2'-bis(3-sulfopropoxy)-4,4'-diaminobi phenyl, 4,4'-bis(4-aminophenoxy)biphenyl-3,3'-disulfonic acid, 3,3'-diaminodiphenylsulfone, etc. are mentioned. Moreover, these diamines can also be used together 2 or more types.

Among the above-mentioned diamines, when an alicyclic diamine such as 3,3'-diaminodiphenylsulfone, bicyclo[2.2.1]heptanebis(methylamine) or trans-1,4-cyclohexanediamine is used, the poly(i) obtained Transparency of the imide is further improved, and fluorine-containing diamines such as 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and 2,2'-bis(trifluoromethyl)benzidine When solvent is used, while the solvent solubility of the polyimide obtained can be improved more remarkably, the low-dielectric conversion of the polyimide obtained becomes possible. When these diamines use together tetracarboxylic dianhydride represented by said Formula (1), and other acid dianhydride, it is 0.9- normally with respect to 1 mol of all acid dianhydrides which also contained other acid dianhydride. From the viewpoint of increasing 1.1 mol and polymerization degree, preferably 0.95 to 1.05 mol is used.

Moreover, a general acid dianhydride can be used together as a copolymerization component as needed. As acid dianhydride which can be used in combination, for example, pyromellitic anhydride, oxydiphthalic dianhydride, biphenyl-3,4,3',4'-tetracarboxylic dianhydride, benzophenone-3,4,3 ',4'-tetracarboxylic dianhydride, diphenylsulfone-3,4,3',4'-tetracarboxylic dianhydride, 4,4'-(2,2-hexafluoroisopropylidene) Diphthalic dianhydride, m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, cyclo Butane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentanetricarboxylic acid-2,6:3,5-2 acid anhydride, cyclohexane- 1,2,4,5-tetracarboxylic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride, 4-phenylethynylphthalic anhydride, naphthalene-1,4,5,8- tetracarboxylic dianhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene, etc. are illustrated, and these acid dianhydrides are two types It can also be used together more than one. When using together another acid dianhydride, the usage-amount of other acid dianhydride in all the acid dianhydrides becomes like this. Preferably it is 10 weight% or more, More preferably, it is 30 weight% or more, On the other hand, Preferably it is 90 weight%. % or less, more preferably 70 weight% or less. By using 10 weight% or more of another acid dianhydride, the physical-property improvement effect by using together the other acid dianhydride mentioned later can fully be acquired. On the other hand, by making the usage-amount of another acid dianhydride into 90 weight% or less, the characteristic derived from the structure of tetracarboxylic dianhydride represented by said Formula (1) is fully exhibited.

As an effect of using other acid dianhydride in combination, for example, polyimide obtained by using together fluorinated acid dianhydride such as 4,4'-(2,2-hexafluoroisopropylidene)diphthalic dianhydride. It is possible to reduce the dielectric constant of Moreover, when acid dianhydrides, such as pyromellitic anhydride which have rigid frame|skeleton, are used together, the heat resistance improvement of the polyimide obtained becomes possible.

When manufacturing a polyamic acid, as a solvent which can be used, tetracarboxylic dianhydride and diamines represented by said Formula (1) which are raw material monomers can be melt|dissolved, Moreover, it is inactive with respect to these raw materials and the polyamic acid to produce|generate. If it is, it will not specifically limit. Examples of such a solvent include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methyl-2-pyrrolidone, butyl acetate, ethyl acetate, and isobutyl acetate. Chain ester solvents, cyclic ester solvents such as γ-butyrolactone, γ-caprolactone and ε-caprolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, triethylene glycol, ethyl cellosolve, butyl cello Solve, propylene glycol methyl acetate, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, dimethoxyethane, diethoxyethane, glycol solvents such as diethylene glycol, phenol, o-cresol, Phenolic solvents such as m-cresol, p-cresol, 3-chlorophenol and 4-chlorophenol, ether solvents such as tetrahydrofuran, dibutyl ether, and diethyl ether, methyl isobutyl ketone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methyl ethyl ketone, acetone and acetophenone, alcohol solvents such as butanol and ethanol, aromatic solvents such as xylene, toluene, and chlorobenzene, sulfone solvents such as sulfolane, dimethyl sulfoxide Side, etc. can be used. Preferably, an amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-pyrrolidone is exemplified. You may use these solvent 1 type or in mixture of 2 or more types as needed.

The amount of the solvent used is such that the total concentration (monomer concentration) of the monomer components (tetracarboxylic dianhydride + diamines) in the reaction system is usually 5 to 40% by weight, preferably 8 to 25% by weight. By superposing|polymerizing in the monomer concentration range mentioned above, the polyamic-acid solution of uniform and high polymerization degree can be obtained. In addition, when polymerization is carried out at a concentration lower than the monomer concentration range, the polymerization degree of the polyamic acid does not become sufficiently high, and the finally obtained polyimide film may become brittle. When polymerization is carried out at a concentration higher than the monomer concentration range, the monomer is When it does not fully dissolve, or a reaction solution becomes non-uniform|heterogenous, it may gelatinize. The solution of the polyamic acid which has the repeating unit represented by said Formula (2) obtained by said method is normally used in the polyimidization process mentioned later in the state of a solution.

<The polyimide which has a repeating unit represented by said Formula (3), and its manufacturing method>

The polyimide having a repeating unit represented by the formula (3) of the present invention is produced by subjecting the polyamic acid having a repeating unit represented by the formula (2) obtained by the above method to a dehydration ring closure reaction (imidization reaction) can do. As a method of imidation reaction, the thermal imidation method and the chemical imidation method are illustrated, for example.

First, the thermal imidization method will be described in detail. The thermal imidation method is performed by first casting|flowing the polymerization solution of a polyamic acid on a glass plate, heating in vacuum or in inert gas, such as nitrogen, or in air, and obtaining a polyamic-acid film. Specifically, for example, in oven, it is 50-190 degreeC normally, Preferably the film of a polyamic acid can be obtained by drying at 100-180 degreeC.

Then, the film of the obtained polyamic acid is 200-400 degreeC normally on a glass plate, Preferably it heats at 250-350 degreeC. Thereby, imidation reaction occurs and a polyimide film can be obtained. As for heating temperature, 200 degreeC or more is preferable from a viewpoint of fully implementing imidation reaction, and 400 degrees C or less is preferable from a viewpoint of the thermal stability of the produced|generated polyimide film.

The imidation reaction is preferably carried out in vacuum or in an inert gas, but as long as the imidization reaction temperature is not too high, it may be carried out in air.

Then, the chemical imidation method is demonstrated in detail. In the chemical imidization method, first, the same solvent as in polymerization is added to the polyamic acid solution having the repeating unit represented by the formula (2) of the present invention obtained by the above method to obtain a suitable solution viscosity that is easy to stir, while stirring, Chemical imidation by adding an organic acid anhydride and a dehydrating ring-closing agent (these two types may be collectively referred to as a chemical imidizing agent), and stirring at a temperature of 0 to 100°C, preferably 10 to 50°C, for 1 to 72 hours. can be completed.

Examples of organic acid anhydrides usable for chemical imidization include acetic anhydride and propionic anhydride. Among these organic acid anhydrides, acetic anhydride is preferable from the viewpoints of handling and separation. Moreover, as a dehydrating ring closure agent, pyridine, triethylamine, quinoline, etc. can be used. Among these dehydrated ring closure agents, pyridine is preferred from the viewpoint of handling and ease of separation. The amount of organic acid anhydride in the chemical imidizing agent is preferably in the range of 1 to 10 moles of the theoretical dehydration amount of the polyamic acid, more preferably 2 to 10 moles. The amount of the dehydrated ring closure agent is preferably in the range of 0.1 to 5 moles, more preferably 1 to 5 moles, based on the amount of the organic acid anhydride.

In the reaction solution obtained by the above chemical imidization method, since by-products such as unreacted chemical imidization agent and organic acid (hereinafter referred to as impurities) are mixed, these may be removed to isolate and purify the polyimide. A known method can be used for purification. For example, after the imidized reaction solution is dripped into a poor solvent to precipitate polyimide, the polyimide powder is recovered, washed repeatedly until impurities are removed, and dried to obtain a polyimide powder. can do. As a solvent that can be used as a poor solvent, polyimide is precipitated, impurities can be efficiently removed, and any solvent that is easy to dry is sufficient. For example, water, alcohols such as methanol, ethanol, and isopropanol are preferable; You may mix and use these.

When the concentration of the polyimide solution at the time of precipitation by dropwise addition into the poor solvent is too high, the precipitated polyimide becomes a particle agglomeration, when impurities remain in the particle agglomeration, or when the obtained polyimide powder is re-dissolved in a solvent. It may take a long time. Therefore, the density|concentration of the polyimide solution at the time of dripping in a poor solvent becomes like this. Preferably it is 20 weight% or less, More preferably, it is 10 weight% or less. Moreover, 1 weight time or more is preferable with respect to the polyimide solution, and, as for the usage-amount of a poor solvent, 1.5-10 weight times is more preferable.

The temperature at the time of collect|recovering the obtained polyimide powder and removing a residual solvent by vacuum drying, hot air drying, etc. will not be restrict|limited, if it is a temperature at which a polyimide does not change in quality, for example, it is 30-150 degreeC.

When the polyimide powder having the repeating unit represented by the formula (3) obtained in this way is used as a polyimide film, the polyimide powder having the repeating unit represented by the formula (3) is first dissolved in a solvent to obtain a polyimide solution. There is a need. As a usable solvent, a solvent in which polyimide powder is dissolved may be used appropriately according to the intended use or processing conditions, and specifically, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N -amide solvents such as methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone , ester solvents such as butyl acetate, ethyl acetate, isobutyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether, phenol, m- Phenolic solvents such as cresol, p-cresol, o-cresol, 3-chlorophenol and 4-chlorophenol, cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone, etc. In addition to ether solvents such as ketone solvents, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, diethoxyethane, and dibutyl ether, acetophenone, 1,3-dimethyl-2-imidazolidinone, alcohol Poran, dimethyl sulfoxide, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, butanol, ethanol, xylene, toluene, A general-purpose solvent such as chlorobenzene, turpentine, mineral spirits, or petroleum naphtha can also be used, and these solvents may be used alone or as a mixture of two or more. The dissolution method of polyimide powder can melt|dissolve in the temperature range below the boiling point of a solvent from room temperature in air or an inert gas, and can be set as a polyimide solution.

A polyimide film can be obtained by casting|flow_spreading the polyimide solution obtained in this way, for example on a glass plate, heating in vacuum, in inert gas, such as nitrogen, or in air, and removing a solvent. For example, a polyimide film can be obtained by drying at 200-400 degreeC normally in oven, Preferably it is 250-350 degreeC. Although it is preferable to carry out polyimide film manufacture in vacuum or inert gas, as long as the temperature is not too high, it does not interfere even if it carries out in air.

It is preferable that the molecular weight of the polyimide which has a repeating unit represented by said Formula (3) obtained by the above-mentioned method is 10,000-600,000 by the weight average molecular weight obtained by the measuring method mentioned later, and it is 20,000-500,000 It is more preferable, and it is still more preferable that it is 40,000-400,000. If the molecular weight of the polyimide is 10,000 or more, it can be molded and it is easy to maintain good mechanical properties. Moreover, when the molecular weight of a polyimide is 400,000 or less, when synthesize|combining, it is easy to control molecular weight, and it is easy to obtain a solution of suitable viscosity, and handling is easy in many cases. In addition, the molecular weight of the polyimide may be based on the viscosity of the polyimide solution.

The polyimide having a repeating unit represented by the formula (3) of the present invention obtained by the method described above has excellent solvent solubility, exhibits a high refractive index with a refractive index of 1.65 or more, and has a glass transition temperature of 260° C. or more and is heat resistant. This is excellent. Furthermore, depending on the combination with the diamine to be used, it becomes a polyimide which also has characteristics such as low dielectric constant and high transparency.

Example

Although the Example of this invention is shown below, this invention is not limited to these. Each physical property value shown in each Example and a comparative example is the result of measurement by the following measuring apparatus and conditions.

[1] NMR measurement

¹ H-NMR, ¹³ C-NMR were recorded by a JEOL-ESC400 spectrometer using tetramethylsilane as internal standard and heavy DMSO as solvent.

[2] LC-MS measurement

Separation and mass spectrometry were carried out under the following measurement conditions to identify the target.

Device: “Xevo G2 Q-Tof” manufactured by Waters Co., Ltd.

·Column: ACQUITY UPLC BEHC18,

(1.7 μm, 2.1 mmφ × 100 mm),

·Column temperature: 40 ℃,

Detection wavelength: UV 220-500 nm,

Mobile phase: A solution = 0.1% formic acid water, B solution = acetonitrile,

·Mobile phase flow rate: 0.3 ㎖/min,

·Mobile phase gradient: B solution concentration: 80% (0 min) → 80% (10 min) → 100% (15 min),

Detection method: Q-Tof,

·Ionization method: APCI (-) method,

·Ion Source: temperature 120 ℃,

Sampling Cone: Voltage 50 V, gas flow 50 ℓ/h,

·Desolvation Gas: temperature 500 ℃, gas flow 1000 ℓ/h.

[3] HPLC purity

The area percentage value when high performance liquid chromatography (HPLC) measurement was performed under the following measurement conditions was made into the purity of each compound.

・Device: L-2130 manufactured by Hitachi, Ltd.

·Column: ZORBAX CN (5 μm, 4.5 mmφ × 250 mm),

·Column temperature: 40 ℃,

Detection wavelength: UV 254 nm,

Mobile phase: A solution = hexane, B solution = tetrahydrofuran,

·Mobile phase flow rate: 1.0 ㎖/min,

- Mobile phase gradient: A solution concentration: 85% (0 minutes) → 60% (35 minutes later) → 0% (40 minutes later).

[4] Weight average molecular weight of polyamic acid

The weight average molecular weight was measured under the following measurement conditions. (in terms of polystyrene)

Device: HLC-8320GPC manufactured by Tosoh Co., Ltd.

·Column: TSK-GEL Super AWM-H (6.0 mml. D. × 15 cm),

· Mobile phase: N,N-dimethylformamide, flow rate: 0.6 ㎖/min,

·Column temperature: 40 ℃.

[5] Measurement of melting point

Using a differential scanning calorimeter ("EXSTAR DSC 7020C" manufactured by SI Nanotechnology Co., Ltd.), the melting endothermic maximum temperature detected when measured at a temperature increase rate of 10°C/min was taken as the melting point.

[6] Measurement of glass transition temperature (Tg)

It was measured using a differential scanning calorimeter ("EXSTAR DSC 7020" manufactured by SI Nanotechnology Co., Ltd.) at a temperature increase rate of 30°C/min, and the point of intersection of the tangent to the inflection point was defined as the glass transition temperature.

[7] Measurement of cutoff wavelength

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

[8] Measurement of light transmittance (T _{400 )}

The transmittance at 400 nm of the polyimide film was measured using a spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation). Transparency of a polyimide film|membrane is so favorable that the transmittance|permeability is high.

[9] Measurement of refractive index (n _in ) and dielectric constant (ε)

Using an Abbe refractometer (“multi-wavelength Abbe refractometer DR-M2” manufactured by Atago Co., Ltd.), the refractive index (wavelength: 589 nm) _in the direction parallel to the polyimide film (n in ) and perpendicular to the direction (n _{out ) was measured.} It measured and the average refractive index ( _nav ) of a polyimide film was calculated|required by following formula.

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

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

ε = 1.1 × n _av ²

[10] Measurement of tensile elongation

Using a tensile tester ("Autograph AGS-X" manufactured by Shimadzu Corporation), a tensile test (tensile speed of 10 mm/min) was performed on a polyimide film test piece (dumbbell-type test piece parallel to 5 mm x 20 mm). Thus, the tensile elongation (%) of the film was determined.The higher the tensile elongation, the higher the toughness of the film.

[11] Solvent solubility

20 mg of the obtained polyimide film or powder was mixed with N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), cyclopentanone (CPN), γ-buty It was put into 1 ml of lolactone (GBL) and the solubility was tested. Solvent solubility was evaluated based on the following criteria.

○: It dissolves at room temperature.

(triangle|delta): When heated, it melt|dissolves, and even if it cools to room temperature, it does not precipitate.

×: Insoluble.

1. Production example of acid dianhydride represented by said Formula (1)

<Example 1>

11.0 g (52.2 mmol) of trimellitic anhydride chloride, 20.0 g of acetonitrile, 10.0 g of toluene, 9,9-bis(4-(4) in a 1 L 4-neck flask equipped with a thermometer, a dropping funnel, and a stirring bar -Hydroxyphenyloxy) phenyl) fluorene (BPOPF) 10.0 g (18.7 mmol) was inject|poured, and it cooled to 2 degreeC after stirring. After cooling, 4.1 g (51.8 mmol) of pyridine was further added dropwise at 2°C to 7°C. After the dropwise addition, the temperature was raised to 25°C, and crystals started to precipitate when the temperature was raised and stirred at the same temperature for 1 hour. Therefore, 10.0 g of acetonitrile and 5.0 g of toluene were added, followed by stirring for an additional 1 hour. .

After completion of stirring, the crystals were separated by filtration at 25°C, and yellow crystals were obtained by further washing the crystals with acetonitrile. The yellow crystal was vacuum-dried at 80 degreeC, and 11.6 g (yield 70.2%, purity 99.4%) of tetracarboxylic dianhydride of the said Formula (1) was obtained.

^{From the <1>} H-NMR spectrum shown in FIG. 1, the ¹³ C-NMR spectrum shown in FIG. 2, and the mass spectrometry chart shown in FIG. 3, it confirmed that the obtained product was tetracarboxylic dianhydride represented by said Formula (1). ^{Hereinafter, 1} H-NMR and ¹³ C-NMR of the obtained tetracarboxylic dianhydride represented by Formula (1) are described in detail.

¹ H-NMR (DMSO-d ₆ ) chart of the obtained tetracarboxylic dianhydride represented by Formula (1) is shown in FIG. 1 . Here, the peak from 8.26 to 8.64 ppm is hydrogen on the benzene ring derived from trimellitic acid, the peak to 7.35 to 7.96 ppm is hydrogen from the benzene ring of the fluorenone skeleton, and the peak to 6.95 to 7.43 ppm is 4-(4 -Hydroxyphenyloxy) belongs to the hydrogen on the benzene ring of the phenyl group. In addition, the peak observed at 2.5 ppm is derived from DMSO as a solvent, and the peak observed at 3.3 ppm is derived from water contained in DMSO.

^{A 13} C-NMR (DMSO-d ₆ ) chart is shown in FIG. 2 . Here, 164.0 to 168.9 ppm and 139.95 to 156.02 ppm are carbon derived from trimellitic anhydride skeleton, 118.8 to 138.83 ppm are derived from the benzene ring of 9,9-bis(4-(4-hydroxyphenyloxy)phenyl)fluorene The peak at carbon of 64.4 ppm is attributed to the carbon at position 9 of fluorenone. In addition, the peak observed at 39.2-40.5 ppm is a thing derived from DMSO of a solvent.

The mass spectrum value and melting|fusing point of the obtained tetracarboxylic dianhydride represented by said Formula (1) are as follows.

Mass spectrum value (M-·): 882.17,

Melting Point (DSC): 193 °C.

2. Production example of the polyamic acid which has a repeating unit represented by said Formula (2), and the polyimide which has a repeating unit represented by said Formula (3)

<Example 2>

(Of the tetracarboxylic dianhydride and 9,9-bis (4-aminophenyl) fluorene represented by the said Formula (1) among the polyamic acids represented by the said Formula (2) (Hereinafter, it may call FDA)) Production example of the polyamic acid obtained from reaction (it is called polyamic acid which has a repeating unit represented by following formula (2-A))

[Formula 6]

5.0 g (5.66 mmol) of tetracarboxylic dianhydride represented by the formula (1) obtained in Example 1 and 2.0 g (5.66 mmol) of FDA were dissolved in 80.2 g of N,N-dimethylacetamide at room temperature, After heating up to 100 degreeC, it confirmed that the solution became uniform, and after standing to cool, it was made to react at room temperature for 24 hours, and the polyamic acid which has a repeating unit represented by the said Formula (2-A) was synthesize|combined. The weight average molecular weight (Mw) of the polyamic acid was 335 and 368.

<Example 3>

(Of the polyimide represented by the formula (3), a polyimide having a repeating unit represented by the following formula (3-A) by chemical imidization of a polyamic acid having a repeating unit represented by the formula (2-A) Produce)

[Formula 7]

5.8 g of acetic anhydride and 2.2 g of pyridine were added to 87.2 g of N,N-dimethylacetamide solution of polyamic acid which has a repeating unit represented by the said Formula (2-A) obtained in Example 2, and it stirred at room temperature for 24 hours By doing so, the N,N-dimethylacetamide solution of the polyimide which has a repeating unit represented by the said Formula (3-A) was obtained.

A polyimide having a repeating unit represented by the formula (3-A) is obtained by dropping the obtained N,N-dimethylacetamide solution of a polyimide having a repeating unit represented by the formula (3-A) in 250 g of methanol. precipitated. The precipitated polyimide was separated by filtration, and after washing with methanol, it was dried to obtain 7.2 g of a pale yellow polyimide powder.

The N,N-dimethylacetamide solution of the polyimide which has a repeating unit represented by the said Formula (3-A) by adding 28.3 g of N,N- dimethylacetamides to 5.0 g of obtained polyimide powder, and stirring until it becomes uniform. got After apply|coating this solution on a glass plate, it heated at 150 degreeC for 1 hour and 250 degreeC for 1 hour, and obtained the thin film of the polyimide which has a repeating unit represented by said Formula (3-A). The film thickness of the thin film was about 19 mu m.

The glass transition temperature of the polyimide films are shown in Table 1 (Tg), the cut-off wavelength, transmittance in the ₄₀₀ ㎚ (T 400), the refractive index (n _in), dielectric constant (ε), shows the results of measurement of tensile elongation. Moreover, the solubility with respect to various solvents is shown in Table 2.

<Example 4>

(Among the polyamic acids represented by the formula (2), tetracarboxylic dianhydride represented by the formula (1) and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (another name 2,2'-bis(trifluoromethyl)benzidine) (hereinafter, may be referred to as TFMB) obtained from the reaction of a polyamic acid (hereinafter, polyamic acid having a repeating unit represented by formula (2-B)))

[Formula 8]

5.0 g (5.66 mmol) of tetracarboxylic dianhydride represented by the formula (1) obtained in Example 1 and 1.8 g (5.66 mmol) of TFMB were dissolved in 16.8 g of N,N-dimethylacetamide at room temperature Then, stirring was performed at room temperature. Since the viscosity increased as the reaction progressed, the repeating unit represented by the above formula (2-B) was stirred at room temperature for 25 hours while appropriately adding N,N-dimethylacetamide (total addition amount: 52.0 g). A N,N-dimethylacetamide solution of polyamic acid having a was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 537,315.

<Example 5>

(Of a polyimide having a repeating unit represented by the following formula (3-B) by chemical imidization of a polyamic acid having a repeating unit represented by the formula (2-B) among the polyimides represented by the formula (3) Produce)

[Formula 9]

5.8 g of acetic anhydride and 2.2 g of pyridine were added to 92.3 g of a N,N-dimethylacetamide solution of a polyamic acid having a repeating unit represented by the formula (2-B) obtained in Example 4, followed by stirring at room temperature for 24 hours , a N,N-dimethylacetamide solution of a polyimide having a repeating unit represented by the formula (3-B) was obtained.

By dripping the obtained N,N- dimethylacetamide solution of the polyimide which has a repeating unit represented by said formula (3-B) in 250 g of methanol, the polyimide which has a repeating unit represented by said formula (3-B) is deposited made it The deposited polyimide was separated by filtration, and after washing with methanol, it was dried to obtain 6.8 g of white polyimide powder.

The N,N-dimethylacetamide solution of the polyimide which has a repeating unit represented by the said Formula (3-B) by adding 45.0 g of N,N- dimethylacetamide to 5.0 g of obtained polyimide powder, and stirring until it becomes uniform. got After apply|coating the obtained solution on a glass plate, it heated at 150 degreeC for 1 hour, and 250 degreeC for 1 hour, and obtained the thin film of the polyimide which has a repeating unit represented by said Formula (3-B). The film thickness of the thin film was about 14 mu m.

The glass transition temperature of the polyimide films are shown in Table 1 (Tg), the cut-off wavelength, transmittance in the ₄₀₀ ㎚ (T 400), the refractive index (n _in), dielectric constant (ε), shows the results of measurement of tensile elongation. Moreover, the solubility with respect to various solvents is shown in Table 2.

3. About the production example of the polyimide derived from the acid dianhydride which has other fluorene skeleton, and the physical property of this polyimide

<Reference Example 1>

(The manufacture example of the polyimide which has a repeating unit represented by following formula (7) obtained from acid dianhydride and TFMB represented by following formula (6))

[Formula 10]

Equation (6):

[Formula 11]

5.0 g (6.88 mmol) of tetracarboxylic dianhydride represented by and 2.2 g (6.88 mmol) of TFMB were dissolved in 17.8 g of N,N-dimethylacetamide at room temperature, and reacted at room temperature for 24 hours to obtain polyamic acid A solution of N,N-dimethylacetamide was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 66,029.

11.0 g of N,N-dimethylacetamide, 7.0 g of acetic anhydride, and 2.7 g of pyridine are added to 25.0 g of the N,N- dimethylacetamide solution of the obtained polyamic acid, and stirred at room temperature for 22 hours, to the said Formula (7) An N,N-dimethylacetamide solution of a polyimide having the repeating unit shown was obtained.

The polyimide which has a repeating unit represented by the said Formula (7) was deposited by dripping the obtained N,N- dimethylacetamide solution of the polyimide which has a repeating unit represented by the said Formula (7) in 250 g of methanol. The deposited polyimide was filtered, and after washing|cleaning with methanol, it dried and obtained 6.6 g of white polyimide powders.

The N,N-dimethylacetamide solution of the polyimide which has a repeating unit represented by the said Formula (7) was obtained by adding 20.0 g of N,N- dimethylacetamide to 5.0 g of obtained polyimide powder, and stirring until it became uniform. . After apply|coating the obtained solution on a glass plate, it heated at 150 degreeC for 1 hour, and 250 degreeC for 1 hour, and obtained the thin film of the polyimide which has a repeating unit represented by said Formula (7). The film thickness of the thin film was about 25 mu m.

The glass transition temperature of the polyimide films are shown in Table 1 (Tg), the cut-off wavelength, transmittance in the ₄₀₀ ㎚ (T 400), the refractive index (n _in), dielectric constant (ε), shows the results of measurement of tensile elongation.

Claims (4)

Equation (1):
[Formula 1]

Tetracarboxylic dianhydride represented by Equation (2) below:
[Formula 2]

(Wherein, Z represents a structural moiety other than the _{amino group (-NH 2} ) of at least one diamine selected from the group consisting of aromatic diamines, aliphatic diamines, and alicyclic diamines)
A polyamic acid having a repeating unit represented by Equation (3) below:
[Formula 3]

(Wherein, Z represents a structural moiety other than the _{amino group (-NH 2} ) of at least one diamine selected from the group consisting of aromatic diamines, aliphatic diamines, and alicyclic diamines)
A polyimide having a repeating unit represented by Trimellitic anhydride halide and the formula (4):
[Formula 4]

The manufacturing method of tetracarboxylic dianhydride of Claim 1 in which the bisphenol represented by is made to react.

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