TW201335126A - 4,4'-sulfonyl diphenyl ester acid dianhydride, method for producing same, and polyimide - Google Patents

Abstract

The purpose of the invention is to provide a polyimide offering excellent solubility in organic solvents, an acid dianhydride compound that is a monomer thereof, and a method for producing the same. An acid dianhydride represented by formula [1], a method for producing the same, and a polyimide. (R1, R2, and R3 each independently represent a hydrogen atom or a C1-20 alkyl group. R4, R5, R6, R7, R8, R9, R10, and R11 each independently represent a hydrogen atom, a C1-20 alkyl group, or a C1-20 haloalkyl group. R4 and R5, R6 and R7, R8 and R9, or R10 and R11 may together form an alkylene chain.)

Description

4,4'-sulfonyldiphenyl ester type acid dianhydride, process for producing the same, and polyimine

The present invention relates to 4,4'-sulfonyldiphenyl ester type acid dianhydride, a process for producing the same, and a polyimine. For further details, for example, it is suitable for a polyimine suitable for use as an electronic material. 4,4'-sulfonyldiphenyl ester type acid dianhydride as a raw material monomer.

Generally, polyimine resin is widely used as a liquid crystal display element or a semiconductor as a protective material, an insulating material, a color filter, etc., for its high mechanical strength, heat resistance, insulation, and solvent resistance. material. In addition, it has recently been expected to be used as a material for optical communication such as a material for optical waveguides.

In recent years, the development of this field has been extremely remarkable, and correspondingly, it has become an increasingly complex feature of the materials used. That is, it is not only excellent in heat resistance and solvent resistance, but also expected to have many composite properties for the respective applications.

However, polyimine, especially at present as a representative example of a wholly aromatic polyimine resin, is composed of pyromellitic anhydride (PMDA) and 4,4'-diaminodiphenyl ether (ODA). The produced polyimine (Kapton: trade name) cannot be used as a solution lacking in solubility, and thus is obtained by dehydration reaction by heating by a precursor called polylysine.

Solvent-soluble polyimine (hereinafter referred to as soluble poly Anthraquinone-based or lactone-based organic solvents such as N-methyl-2-pyrrolidone (NMP) or γ-butyrolactone which have been widely used in the past, because of their high boiling point, In order to remove the solvent, high temperature firing cannot be avoided.

In the field of liquid crystal display devices, research and development of flexible liquid crystal display devices using plastic substrates have been carried out in recent years, and it has become a problem in the case of high-temperature firing because the component constituent components have deteriorated, and in recent years, it has been desired to be low-temperature firing.

On the other hand, polylysine which exhibits high solvent solubility also has a problem that volume change is likely to occur due to the inability to obtain sufficient liquid crystal display characteristics due to sulfhydrylation, so that it is converted to a desired low boiling point. The organic solvent is a soluble polyimine.

As a solution for this decision, a synthesis method using a tetracarboxylic dianhydride which is an alicyclic dicarboxylic anhydride which is advantageous for the solubility of an organic solvent is considered. As an example thereof, a diester type acid dianhydride obtained by hydrogenating a trimellitic anhydride chloride and a hydroquinone is known (Patent Document 1). However, it is described as "the polyimine obtained from the acid dianhydride and 4,4'-diaminodianine (ODA) is insoluble in cyclohexanone, and the processability is poor." (Patent Document 2).

So far, the substituted 4,4'-sulfonyldiphenyl ester type acid obtained from the nuclear hydrogenated trimellitic anhydride halide compound and the economically inexpensive and advantageous substitution of the 4,4'-sulfonyldiphenol compound Anhydride is not known.

Prior technical literature

Patent literature

[Patent Document 1] WO2006-129771

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-163088

The present invention has been made in view of such a problem, and is intended to provide a 4,4'-sulfonyldiphenyl ester type acid dianhydride excellent in solubility in an organic solvent, a process for producing the same, and a polyimine. .

In order to achieve the above object, the inventors of the present invention have succeeded in the determination of the alicyclic dicarboxylic anhydride which is advantageous for the solubility of the organic solvent, and has established an economical and inexpensive substitution from the nuclear hydrogenated trimellitic anhydride halide compound. The method for producing a substituted 4,4'-sulfonyldiphenyl ester type acid dianhydride obtained from a 4'-sulfonyl diol compound, and the present invention has been completed in an attempt to induce the polyimine. The resulting tetracarboxylic dianhydride and its polyimine are novel compounds.

That is, the present invention is constituted by the following.

A compound represented by the following formula [1]: (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a haloalkyl group having 1 to 20 carbon atoms; however, R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ Together, an alkylene chain can be formed).

2. The compound according to the above 1, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom.

3. A method for producing a tetracarboxylic dianhydride represented by the following formula [1], which is characterized in that (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 have the} same meanings as defined above). The hydrazine compound represented by the following formula [2] and the nuclear hydrogenated trimellitic anhydride halide represented by the following formula [3] are reacted in the presence of a base: (wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 have the} same meanings as defined above) (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and X represents a halogen atom).

4. The method according to the above 3, wherein the R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom.

5. The production method according to the above 3 or 4, wherein the base is pyridine or triethylamine.

6. A polylysine containing a repeating unit represented by the formula [4]: (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 have the} same meanings as defined above, and A represents a divalent organic group, n represents an integer of 2 or more).

7. The poly-proline as described above, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom.

8. A polyimine containing a repeating unit represented by the formula [5]: (wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 have the} same meanings as defined above, and A represents a divalent The organic group, n represents an integer of 2 or more).

9. The polyimine of 8 above, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom.

According to the present invention, the tetracarboxylic dianhydride of the present invention is excellent in organic solvent solubility of the monomer itself by the effect of the structure of the two alicyclic anhydrides which contribute to the solubility of the organic solvent and the sulfonyl group structure of the polar group. Further, the polyimine obtained from various diamine compounds is also expected to exhibit high solubility in organic solvents.

As a practical scene, it is expected to be suitable for use as an electronic material or the like as a protective material or an insulating material in semiconductors other than the liquid crystal display element.

Hereinafter, the present invention will be described in further detail.

The method for producing 4,4'-sulfonyldiphenyl ester type acid dianhydride (hereinafter abbreviated as SBPCC) represented by the above formula [1] is shown in the following reaction scheme.

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and X have the same meanings as defined above).

That is, the desired SBPCC was produced by condensing a substituted 4,4'-sulfonyl diol compound (SDPC) with a 2 molar substituted hydrogenated trimellitic anhydride halide (DOCH) in the presence of a base.

The amount of DOCH used for SDPC is preferably 2.0 to 3.0 msec, and more preferably 2.0 to 2.5 m.

As the base, an organic base such as pyridine, triethylamine or tripropylamine or a carbonate of an alkali metal such as lithium carbonate, sodium carbonate or potassium carbonate can be used, and in particular, pyridine or triethylamine is preferred. The amount of use is preferably 2.0 to 3.0 moles for SDPC, 2.0 to 2.5 moles, and 2.0 to 2.3 moles.

As the reaction solvent, N,N-dimethylformamide (DMF), tetrahydrofuran (THF) or 1,4-dioxane is preferred. The amount of such use is preferably 3 to 50 mass times for SDPC, and preferably 5 to 30 mass times.

The reaction temperature is about -30 to 150 ° C, preferably 0 to 120 ° C.

The reaction time is preferably from 1 to 50 hours, especially from 2 to 30 hours.

After the reaction, the by-produced salt is removed by filtration, and the filtrate is concentrated. Go to the reaction crude. Here, two layers of the oil of the lower layer and the organic solvent layer of the upper layer are separated by adding a suitable solvent such as ethyl acetate. After the upper organic solvent layer was slightly concentrated, crystals were precipitated as soon as it was ice-cooled. The crystals were filtered and dried under reduced pressure to give the first crystals of the objective.

Further, ethyl acetate was added to the lower layer to dissolve it by heating, and after cooling with water, it was concentrated by washing with water to obtain a gum. Then, acetic anhydride is added and stirred in an oil bath of 100 to 150 ° C for 10 to 60 minutes, and then concentrated, and further dried under reduced pressure to obtain a second crystal of the object.

The reaction can be carried out under normal pressure or under pressure, and can also be batch or continuous.

As a raw material SDPC, various substituents can be introduced.

Here, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a haloalkyl group having 1 to 20 carbon atoms. . However, R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ become together, and the formation of an alkylene chain does not affect.

The alkyl group having 1 to 20 carbon atoms is a specific example of a straight chain and a branch, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and an s group. -butyl, t-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl Base-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl-n -butyl, 1,1,2-trimethyl-n-propyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-dodeyl , n-trideyl, n-tetradecyl, n-pentadepyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadesyl and n-tetradecyl.

Further, each represents that n is positive, i is different, s is second, and t is third.

Examples of the haloalkyl group having 1 to 20 carbon atoms include CF ₃ -, CF ₃ CH ₂ -, CF ₃ CF ₂ -, CF ₃ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₂ -, and CF. ₃ CF ₂ CH ₂ -, CF ₃ (CF ₂ ) ₃ -, CF ₃ CF ₂ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₄ -, CF ₃ (CF ₂ ) ₂ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₅ -, CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₆ -, CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₇ -, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₈ -, CF ₃ (CF ₂ ) ₆ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₉ - , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₁₀ -, CF ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ -, CF ₃ (CF ₂ ) ₁₁ -, CF ₃ ( CF ₂ ) ₁₂ -, CF ₃ (CF ₂ ) ₁₃ -, CF ₃ (CF ₂ ) ₁₄ -, CF ₃ (CF ₂ ) ₁₅ -, CF ₃ (CF ₂ ) ₁₆ -, CF ₃ (CF ₂ ) ₁₇ - And CF ₃ (CF ₂ ) ₁₈ - and CF ₃ (CF ₂ ) ₁₉ - group and the like.

Specific examples of R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ together form an alkylene chain include -(CH ₂ ) ₂ -, -(CH ₂ ). ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, and the like.

As a specific compound, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are hydrogen atoms of 4,4′-sulfonyldiphenol, which is inexpensive. practical.

The other raw material is a substituted nuclear hydrogenated trimellitic anhydride halide (DOCH), and X represents each atom of fluorine, chlorine, bromine and iodine.

For the DOCH, various substituents may be introduced, and each of R ¹ , R ² and R ³ independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

Among these, it is advantageous in that R ¹ , R ² and R ³ are hydrogen atomic hydrogenated trimellitic anhydride halides.

This nuclear hydrogenated trimellitic anhydride halide is obtained by hydrogenating a benzene to a nucleus Tricarboxylic anhydride is obtained by halogenation with various halogenating agents. As an example, by using grasshopper chlorine as a halogenating agent, DOCH is obtained with stable reaction conditions and high recovery rate.

The amount of chlorine used in grasshoppers is preferably 1.0 to 2.0 moles per DOCH, especially 1.0 to 1.5 moles. The reaction temperature is preferably 0 to 60 ° C.

The SBPCC which is described above as the tetracarboxylic dianhydride of the present invention, after being polycondensed with a diamine to form a poly-proline, can be guided to the corresponding polyimine by a dehydration ring reaction using heat or a dehydrating agent.

The SBPCC which is a tetracarboxylic dianhydride of the present invention is given a polyimine which is soluble in a different organic solvent from a kind of a diamine, and gives a polyimine which has excellent solubility to a low-boiling organic solvent.

The diamine is not particularly limited, and various diamines used in the synthesis of the conventional polyimine can be used. Specific examples thereof include p-phenylenediamine (hereinafter abbreviated as p-PDA), m-phenylenediamine (hereinafter abbreviated as m-PDA), and 2,5-diaminotoluene. 2,6-Diaminotoluene, 4,4'-diaminodiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl, 3,3'-dimethoxy Base-4,4'-diaminodiphenyl, 4,4'-methylenediphenylamine (hereinafter abbreviated as MDA), 4,4'-diaminodiphenyl ether (hereinafter, abbreviated as ODA), 2 , 2'-diaminodiphenylpropane, bis(3,5-diethyl-4-aminephenyl)methane, diaminodiphenyl hydrazine, diaminobenzophenone, diaminonaphthalene, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, bis(4-aminophenoxy)pentane (hereinafter, abbreviated as BAPP), 9, 10-bis(4-aminophenyl) onion, 4,4'-(1,3-phenylenedioxy)diphenylamine (hereinafter, abbreviated as PODA), 3,5-diamino-1,6- Dimethoxy Benzobenzene, 3,5-diamino-1,6-dimethoxytoluene, 4,4'-bis(4-aminephenoxy)diphenylhydrazine, 2,2-bis[4-(4- An aromatic diamine such as an amine phenoxy)phenyl]propane or a 2,2'-trifluoromethyl-4,4'-diaminodiphenyl group; 4,4'-methyl bis(cyclohexane) Amine), 4,4'-methyl bis(2-methylcyclohexylamine), bis(4-aminocyclohexyl)ether, bis(4-amino-3-methylcyclohexyl)ether, double (4-Aminocyclohexyl) sulfide, bis(4-amino-3-methylcyclohexyl) sulfide, bis(4-aminocyclohexyl)anthracene, bis(4-amino-3-methyl) Cyclohexyl) hydrazine, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-amino-3-methylcyclohexyl)propane, bis(4-aminocyclohexyl)di An alicyclic diamine such as methyl decane or bis(4-amino-3-methylcyclohexyl)dimethyl decane; tetramethylammonium, hexamethylenediamine and 3,3'-( An aliphatic diamine or the like such as dimethylnonanediyl)bis(oxy)dipropan-1-amine. These diamines can be used alone or in combination of two or more.

Further, in the above formulae [4] and [5], A is a divalent organic group derived from a diamine to be used.

In the present invention, among the total molar numbers of the tetracarboxylic dianhydride used, at least 10 mol% of the SBPCC of the formula [1] is preferred.

Further, the tetracarboxylic acid compound and its derivative used in the usual polyimine synthesis can also be used at the same time.

Specific examples thereof include 1,2,3,4-cyclobutanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid. 3,4-dicarboxy-1-cyclohexyl succinic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3.3.0]octane-2 An alicyclic tetracarboxylic acid such as 4,6,8-tetracarboxylic acid or the like and an acid dianhydride thereof, and a dicarboxylic acid diacid halide or the like.

Further, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6- may also be mentioned. Naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-onion tetracarboxylic acid, 1,2,5,6-onion tetracarboxylic acid, 3,3',4 , 4'-diphenyltetracarboxylic acid, 2,3,3',4'-diphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)ether, 3,3',4,4' - benzophenone tetracarboxylic acid, bis(3,4-dicarboxyphenyl)methane, 2,2-bis(3,4-dicarboxyphenyl)propane, 1,1,1,3,3,3 -hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)dimethylnonane, bis(3,4-dicarboxyphenyl)diphenyl An aromatic tetracarboxylic acid such as decane, 2,3,4,5-pyridinetetracarboxylic acid or 2,6-bis(3,4-dicarboxyphenyl)pyridine, and the like, and such acid dianhydrides, and the like Dicarboxylic acid diacid halides and the like. In addition, these tetracarboxylic acid compounds may be used alone or in combination of two or more.

The method for obtaining the polyproline of the present invention is not particularly limited, and the tetracarboxylic dianhydride and its derivative may be reacted with a diamine by a known method and polymerized.

The ratio of the molar number of the total tetracarboxylic dianhydride to the molar number of the total diamine compound in the case of synthesizing polyamic acid is preferably carboxylic acid compound/diamine compound = 0.8 to 1.2. As with the usual polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the resulting polymer. When the degree of polymerization is too small, the strength at the time of film-forming polyimine is insufficient, and when the degree of polymerization is too large, the workability at the time of forming a polyimide film may deteriorate.

Therefore, the degree of polymerization of the reaction product is 0.05 to 5.0 dl/g in terms of the reducing viscosity of the polyaminic acid solution (in a concentration of 0.5 g/N-methyl-2-pyrrolidone at 30 ° C / Dl) is better.

The number average molecular weight (Mn) of the polyglycolic acid of the present invention is preferably from 1,000 to 30,000, more preferably from 2,000 to 20,000. Again, the weight average The sub-quantity (Mw) is preferably 1,500 to 50,000, more preferably 3,000 to 40,000. Further Mw/Mn is preferably 1.5 to 2.5.

Further, in the above formulae [4] and [5], in order to maintain the solubility of the organic solvent of the polyglycolic acid or the polyimine, it is preferably 100 or less, more preferably 3 to 30.

The polylysine of the present invention is a polyamine containing a repeating unit represented by the above formula [4], and the content of the repeating unit represented by the above formula [4] is preferably 10 to 100% by mass of polyglycine. More preferably, 100% by mass of polyamic acid is used.

Examples of the solvent used for the synthesis of the polyamic acid include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) and N,N-dimethylformamide (hereinafter abbreviated as DMF). N,N-dimethylacetamide (hereinafter abbreviated as DMAc), m-cresol, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, Hexamethylphosphoniumamine, γ-butyrolactone, and the like. These may be used alone or in combination. Further, even if it is a solvent which cannot dissolve polyamic acid, the above solvent can be added in the range which can obtain a uniform solution.

The temperature of the polycondensation reaction is -20 to 150 ° C, and any temperature preferably selected from -5 to 100 ° C can be selected.

The polyimine of the present invention is obtained by subjecting polylysine synthesized as described above to dehydration ring (thermally imidization) by heating. Further, at this time, polylysine is converted into a quinone imine in a solvent, and it can also be used as a solvent-soluble polyimine.

Alternatively, chemical cyclization using a well-known dehydration ring catalyst can also be used. method.

The heating method is 100 to 350 ° C, and any temperature of preferably 120 to 300 ° C can be selected.

The chemical cyclization method can be carried out, for example, in the presence of pyridine or triethylamine or the like, and acetic anhydride or the like. The temperature at this time can be any temperature preferably selected from -20 to 200 °C.

The polyimine solution obtained in this way can be used as it is, and a polybasic imine is precipitated by adding a poor solvent such as methanol, ethanol or water, and the individual can be used as a polyimine powder or the polymerization can be made. The quinone imine powder is redissolved in a suitable solvent.

The solvent for re-dissolving is not particularly limited as long as the obtained polyimine is dissolved, and examples thereof include m-cresol, 2-pyrrolidone, NMP, N-ethyl-2-pyrrolidone, and N- Vinyl-2-pyrrolidone, DMAc, DMF, γ-butyrolactone, 1,4-dioxane, THF, acetonitrile, ethyl acetate, chloroform and the like.

Further, even if the solvent of the polyimine cannot be dissolved alone, it can be added to the above solvent if it does not impair the solubility. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1-methoxy-2-. Propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol- 1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, Ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like.

a polylysine (polyimine precursor) solution prepared as described above It is applied to a substrate, and the polyimine film can be produced by dehydrating and cyclizing the solvent while evaporating by heating, or by applying a polyimine solution to the substrate and evaporating the solvent by heating.

At this time, the heating temperature is usually about 100 to 300 °C.

Further, for the purpose of improving the adhesion between the polyimide film and the substrate, an additive such as a coupling agent may be added to the polyaminic acid solution or the polyimine solution.

The polyimine of the present invention is a polyimine containing a repeating unit represented by the above formula [5], and the content of the repeating unit represented by the above formula [5] is 10 to 100% by mass. Preferably, 100% by mass of the polyimine is particularly preferred.

[Examples]

Hereinafter, the present invention will be specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the examples described below. The measuring device for each physical property in the examples is as follows.

[1][ ¹ H NMR]

Model: Varian NMR System 400NB (400MHz)

Determination of solvent: CDCl ₃ , DMSO-d ₆

Reference material: tetrametheylsilane (TMS)

[2][IR]

Model: Nicolet 6700 FT-IR (Thermo)

Determination method: ATR method (diamond crystal) Decomposition energy: 4.0 cm ^-1 (measurement range: 400 to 4000 cm ^-1 )

Sample scan: 50 times Background scan: 50 times

[3] [melting point (m.p.)] [softening point (PMT)]

Model: Micro melting point measuring device (MP-S3) (manufactured by Yanaco Machine Development Research Institute)

[4] Determination of number average molecular weight and weight average molecular weight: GPC (Gel Permeation Chromatography) method

The weight average molecular weight of the polymer (hereinafter abbreviated as Mw) and the molecular weight distribution were measured by a GPC apparatus (Shodex (registered trademark) column KF803L and KF805L) manufactured by JASCO Corporation, and a flow rate of 1 ml/min was used as a solvent for DMF. The temperature was measured at 50 ° C. Further, Mw is a value converted to polystyrene.

[Reference Example 1] Synthesis of DOCC]

To a four-neck reaction flask of 200 ml, DOCA 17.4 g (88.0 mmol) and THF 105 g were added, and the mixture was stirred with a magnetic stirrer while cooling to 5 ° C on an ice bath. Dissolved. Next, after adding 60 mg of DMF, 13.2 g (104 mmol) of grassy chlorine was dropped over 10 minutes. Further, the mixture was stirred at 20 to 25 ° C for 1 hour from the ice bath. Then, the reaction solution was concentrated under reduced pressure at 60 ° C. Drying gave 19.8 g of a pale yellow oil. This product was identified as 1,3-dimethoxyoctahydroisobenzofuran-5-carbonyl chloride (DOCC) for the purpose of ¹ H NMR.

[Example 1] Synthesis of SBPC]

4,4'-sulfonyl diphenol (SDP) 10.0 g (40.0 mmol), pyridine 8.23 g (10.4 mmol) and THF 80 g were added to a four-neck reaction flask of 200 ml, and the magnetic force was cooled on an ice bath at 5 ° C. While stirring with a stirrer, a solution of 19.8 g (88.0 mmol) of the crude DOCC synthesized in Reference Example 1 dissolved in 30 g of THF was added thereto over 15 minutes. Then, the mixture was stirred at room temperature for 23 hours at 23 ° C in an ice bath, and the stirring was slowed by the formation of a large amount of white solid. Then, 20 g of THF was added, and the mixture was heated to 45 to 50 ° C and further stirred for 5 hours to stop the reaction.

Then, the residue after filtration was washed three times with THF, and then the mixture of the filtrate and the washing liquid was concentrated to obtain 24.0 g of an orange gum. When the crude product was added with 110 g of ethyl acetate at 75 ° C, it was separated into two layers of an organic layer of the upper layer and a gel of the lower layer. After the water was cooled, it was separated into an upper layer and a lower layer, and the organic layer of the upper layer was concentrated to 39 g and then ice-cooled. The white solid was precipitated, washed with ethyl acetate after filtration, dried under reduced pressure at 75 ° C for 2 hours to give residual ethyl acetate, and further dried under reduced pressure at 110 ° C for 2 hours to obtain first white crystals of 6.00 g (Y24). .6%) (mp: 118 ~120 ° C).

This crystal was confirmed by ¹ H NMR and IR for 4,4'-sulfonyl bis(1,4-phenylene)bis(1,3-dimethoxyoctahydroisobenzofuran-5-). Carboxylic ester) (SBPC).

¹ H NMR (DMSO-d ₆ , δ ppm): 1.446-1.539 (m, 2H), 1.682-1.836 (m, 2H), 1.943-1.986 (m, 2H), 2.024-2.070 (m, 2H), 2.330- 2.373 (m, 2H), 2.769-2.820 (m, 2H), 3.324-3.390 (m, 2H), 3.551 (dd, J ₁ = 7.6 Hz, J ₂ = 12.0 Hz, 2H), 7.377 (d, J = 8.8 Hz, 4H), 8.015 (d, J = 9.2 Hz, 1H) IR (cm ^-1 ): 2941.4 (cyclohexane ring CH ₂ stretching), 1860.0 (cyclic acid anhydride C=O stretching), 1779.2 ( Cyclic acid anhydride C=O stretching), 1752.0 (ester C=O stretching), 1586.4 (phenyl CH angle), 1488.3 (cyclohexane ring CH ₂ angle)

Then, 50 g of ethyl acetate and 40 g of water were added to the gel of the lower layer, and the mixture was separated, and the organic layer was washed with water and concentrated to give 8.0 g of a gum. To the gum, 24 g of acetic anhydride was added and stirred in an oil bath at 130 ° C for 1 hour. After concentrating the reaction mixture, it was dried under reduced pressure at 120 ° C for 2 hours to give a pale yellow glassy second crystal of 7.00 g (Y 28.7%) (mp: 85 to 88 ° C). This crystal was also confirmed to be the target SBPC from ¹ H NMR and IR.

[Example 2] Synthesis of SBPC-ODA polyaminic acid and polyimine

The first white crystal SBPC 0.678 g (1.1 mmol) and NMP 3.51 g obtained in Example 1 were placed in a 50 ml four-neck reaction flask equipped with a stirrer at 23 ° C, and dissolved by stirring. Next, to the solution under stirring, 0.200 g (1.0 mmol) of 4,4'-diaminodiphenyl ether (ODA) was added and dissolved by stirring. Then, the polymerization was carried out by stirring at 23 ° C for 20 hours to obtain a polyaminic acid solution having a solid content concentration of 20% by mass. The viscosity of this polymerization solution is 254 mPa. s.

To this solution, 10.2 g of NMP was further added to a polyamic acid solution having a solid content of 6 mass%, and the number average molecular weight (Mn) was 8,851, and the weight average molecular weight (Mw) was 17,758, Mw as a result of GPC measurement. /Mn is 2.01.

Then, 1.02 g (10 mmol) of acetic anhydride and 0.48 g (6 mmol) of pyridine were added to the polyamine acid solution having a solid content of 6 mass%, and the mixture was stirred at 100 ° C for 5 hours. After returning to room temperature, the reaction solution was added dropwise to 60 ml of methanol under stirring, and further stirred for 30 minutes to precipitate a solid. After filtering this, it was washed three times with 30 ml of methanol, and then dried under reduced pressure at 80 ° C for 2 hours to obtain 0.54 g of a white powder of SBPC-ODA polyimine (recovery rate: 69.8%).

PMT: 201~203°C

[Example 3] Synthesis of SBPC-PODA polyaminic acid and polyimine

The first white crystal SBPC 0.678 g (1.1 mmol) and NMP 3.88 g obtained in Example 1 were placed in a 50 ml four-neck reaction flask equipped with a stirrer at 25 ° C, and dissolved by stirring. Next, 0.292 g (1.0 mmol) of 4,4'-(1,3-phenylenedioxy)diphenylamine (PODA) was added to the solution under stirring to dissolve. Then, the polymerization was carried out by stirring at 25 ° C for 6 hours to obtain a polyamic acid solution having a solid content concentration of 20% by mass. The viscosity of the polymerization solution is 208 mPa. s.

To this solution, 11.3 g of NMP was further added to a polyamine solution having a solid content of 6 mass%, and the number average molecular weight (Mn) was 7,982, and the weight average molecular weight (Mw) was 18,478, Mw as determined by GPC. /Mn is 2.31.

Then, the polyamic acid solution having a solid content of 6 mass% was added with 1.02 g (10 mmol) of acetic anhydride and 0.48 g (6 mmol) of pyridine, and the mixture was stirred at 100 ° C for 5 hours. After returning to room temperature, the reaction solution was added dropwise to 67 ml of methanol under stirring, and further stirred for 1 hour to precipitate a solid. After filtering this, it was washed three times with 30 ml of methanol, and then dried under reduced pressure at 80 ° C. 2 hours, 0.60 g of a white powder of SBPC-PODA polyimine (recovery rate 74.3%) was obtained.

PMT: 183~186°C

[Example 4] Synthesis of SBPC-BAPP polyaminic acid and polyimine

The first white crystal SBPC 0.678 g (1.1 mmol) and NMP 3.14 g obtained in Example 1 were placed in a 50 ml four-neck reaction flask equipped with a stirrer at 23 ° C, and dissolved by stirring. Then, 0.286 g (1.0 mmol) of bis(4-aminophenoxy)pentane (BAPP) was added to the solution under stirring. Subsequently, the polymerization was carried out by stirring at 23 ° C for 7 hours and 30 minutes to obtain a polyamic acid solution having a solid content concentration of 20% by mass. The viscosity of this polymerization solution is 359mPa. s.

To the solution, further, 11.3 g of NMP was added to a polyamic acid solution having a solid content of 6 mass%, and the number average molecular weight (Mn) was 8,901, and the weight average molecular weight (Mw) was 19,360, Mw as determined by GPC. /Mn is 2.18.

Then, the polyamic acid solution having a solid content of 6 mass% was added with 1.02 g (10 mmol) of acetic anhydride and 0.48 g (6 mmol) of pyridine at 100 ° C. Mix for 5 hours. After returning to room temperature, the reaction solution was added dropwise to 65 ml of methanol under stirring, and further stirred for 1 hour to precipitate a solid. After filtering this, it was washed three times with 30 ml of methanol, and then dried under reduced pressure at 80 ° C for 2 hours to obtain 0.63 g of a white powder of SBPC/BAPP polyimine (recovery rate: 73.2%).

PMT: 164~166°C

[Example 5] Synthesis of SBPC-MDA polyaminic acid and polyimine

The pale yellow glassy second white crystal SBPC 0.678 g (1.1 mmol) and NMP 3.50 g obtained in Example 1 were placed in a 50 ml four-neck reaction flask equipped with a stirrer at 23 ° C, and stirred. Dissolved. Then, 4,4'-methylenediphenylamine (MDA) 0.198 g (1.0 mmol) was added to the solution under stirring. Subsequently, the polymerization was carried out by stirring at 23 ° C for 16 hours to obtain a polyamidic acid solution having a solid content concentration of 20% by mass. The viscosity of this polymerization solution is 78mPa. s.

To this solution, further, 10.3 g of NMP was added and diluted in a polyamine solution having a solid content of 6 mass%, and the number average molecular weight (Mn) was 4,100 and the weight average molecular weight (Mw) was 8,238 as a result of GPC measurement. Mw/Mn was 2.01.

Then, the polyamic acid solution having a solid content of 6 mass% was added with 1.02 g (10 mmol) of acetic anhydride and 0.48 g (6 mmol) of pyridine, and the mixture was stirred at 100 ° C for 5 hours. After returning to room temperature, the reaction solution was added dropwise to 65 ml of methanol under stirring, and further stirred for 1 hour to precipitate a solid. After filtering this, it was washed three times with 30 ml of methanol, and then dried under reduced pressure at 80 ° C for 2 hours to obtain 0.45 g of a white powder of SBPC/MDA polyimine (recovery rate: 58.3%).

PMT: 194~196°C

[Example 6] Synthesis of SBPC-m-PDA polyaminic acid and polyimine

The first white crystal SBPC 0.678 g (1.1 mmol) and NMP 3.14 g obtained in Example 1 were placed in a 50 ml four-neck reaction flask equipped with a stirrer at 23 ° C, and dissolved by stirring. Then, 0.18 g (1.0 mmol) of m-phenylenediamine (m-PDA) was added to the solution under stirring. Subsequently, the polymerization was carried out by stirring at 23 ° C for 7 hours to obtain a polyamidic acid solution having a solid content concentration of 20% by mass. The viscosity of this polymerization solution is 118mPa. s.

Further, 9.2 g of NMP was added to a polyamine solution having a solid content of 6 mass%, and the number average molecular weight (Mn) was 6,257, and the weight average molecular weight (Mw) was 12,637, Mw as determined by GPC. /Mn is 2.02.

Then, the polyamic acid solution having a solid content of 6 mass% was added with 1.02 g (10 mmol) of acetic anhydride and 0.48 g (6 mmol) of pyridine, and the mixture was stirred at 100 ° C for 5 hours. After returning to room temperature, the reaction solution was added dropwise to 63 ml of methanol under stirring, and further stirred for 30 minutes to precipitate a solid. After filtering this, it was washed three times with 30 ml of methanol, and then dried under reduced pressure at 80 ° C for 2 hours to obtain 0.40 g of a white powder of SBPC/m-PDA polyimine (recovery rate: 58.6%).

PMT: 199~200°C

[Example 7] Synthesis of SBPC-p-PDA polyaminic acid and polyimine

The first white crystal SBPC 0.678 g (1.1 mmol) and NMP 3.14 g obtained in Example 1 were placed in a 50 ml four-neck reaction flask equipped with a stirrer at 23 ° C, and dissolved by stirring. Then, p-phenylenediamine (p-PDA) 0.108 g was added to the solution under stirring. (1.0 mmol). Subsequently, the polymerization was carried out by stirring at 23 ° C for 17 hours to obtain a polyamic acid solution having a solid content concentration of 20% by mass. The viscosity of this polymerization solution is 115mPa. s.

To this solution, 9.2 g of NMP was further added to a polyamine solution having a solid content of 6 mass%, and the number average molecular weight (Mn) was 5,657 as measured by GPC, and the weight average molecular weight (Mw) was 10,578, Mw. /Mn is 1.87.

Then, the polyamic acid solution having a solid content of 6 mass% was added with 1.02 g (10 mmol) of acetic anhydride and 0.48 g (6 mmol) of pyridine, and the mixture was stirred at 100 ° C for 5 hours. After returning to room temperature, the reaction solution was added dropwise to 55 ml of methanol under stirring, and further stirred for 1 hour to precipitate a solid. After filtering this, it was washed three times with 30 ml of methanol, and then dried under reduced pressure at 80 ° C for 2 hours to obtain 0.55 g of a white powder of SBPC/p-PDA polyimine (recovery rate: 80.5%).

PMT: 203~205°C

[Comparative Example 1] Synthesis of PMDA-ODA Polyaminic Acid and Polyimine

To a 50 ml four-neck reaction flask equipped with a stirrer in a room at 22 ° C, ODA 1.00 g (5.0 mmol) and NMP 18.2 g were added and dissolved. Then, the solution was stirred and dissolved while dissolving 1.03 g (4.75 mmol) of pyromellitic dianhydride (PMDA). Further, the mixture was stirred at 20 ° C for 23 hours to carry out a polymerization reaction to obtain a polyaminic acid solution having a solid content concentration of 10% by mass. To the solution, 14 g of NMP was added to a polyamine solution having a solid content of 6 mass%, and the number average molecular weight (Mn) was 2,173, and the weight average molecular weight (Mw) was 4,310, and Mw/Mn was determined by GPC. 1.98.

Then, the polyamic acid solution having a solid content of 6 mass% was added with 5.1 g (50 mmol) of acetic anhydride and 2.37 g (30 mmol) of pyridine, and the mixture was stirred at 100 ° C for 4 hours. After returning to room temperature, the reaction solution was added dropwise to 147 ml of methanol under stirring, and further stirred for 1 hour to precipitate an orange solid. After filtering this, it was washed three times with 50 ml of methanol, and then dried under reduced pressure at 80 ° C for 2 hours to obtain 1.55 g of an orange powder of PMDA-ODA polyimine (recovery rate: 86%).

PMT: >300°C

The organic compounds of the SBPC-diamine polyimine (SBPC-DA-PI) obtained in the above Examples 2 to 7, and the PMDA-DA-polyimine (PMDA-DA-PI) obtained in Comparative Example 1 were organic. Solvent solubility was evaluated by the following procedure. The results are shown in Table 1.

(assay)

5 mg of each polyimine was added to an organic solvent of 100 mg to a specific temperature Stir the mixture to confirm its solubility.

DMSO: dimethyl hydrazine, DMF: N, N-dimethylformamide, THF: tetrahydrofuran, EDC: 1,2-dichloroethane

As shown in Table 1, the SBPC-DA-PI of the present invention obtained in Examples 2 to 7 was a soluble polyimine which was determined to be excellent in dissolving a low-boiling organic solvent in various organic solvents for the first time. On the other hand, PMDA-DA-PI, although low in molecular weight, is insoluble in organic solvents.

[Industry use possibility]

The novel polylysine and polyamidene obtained from the novel compound provided by the present invention are the first low-boiling organic solvents for various organic solvents. Highly soluble. Therefore, it is desirable to utilize the various electronic components that must be fired at a low temperature.

In addition, the entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2011-245091, filed on Nov. 9, 2011, are hereby incorporated by reference. .

Claims (9)

A compound represented by the following formula [1]: (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a haloalkyl group having 1 to 20 carbon atoms; however, R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ It is also possible to form an alkylene chain together). The compound of claim 1, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom. A method for producing a tetracarboxylic dianhydride represented by the following formula [1], which is characterized in that (wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ^{11 have the} same meanings as defined above), and the following formula [2] is used. The ruthenium compound represented by the above formula, and the nuclear hydrogenated trimellitic anhydride halide represented by the following formula [3] are reacted in the presence of a base: (wherein R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen having 1 to 20 carbon atoms. a group; however, R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ may together form an alkylene chain) (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and X represents a halogen atom). The method of claim 3, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom. The process of claim 3, wherein the base is pyridine or triethylamine. A polylysine containing a repeating unit represented by the formula [4]: (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a haloalkyl group having 1 to 20 carbon atoms; however, R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ An alkylene chain may also be formed together; A represents a divalent organic group; n represents an integer of 2 or more). The polyamic acid of claim 6, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom. . A polyimine containing a repeating unit represented by the formula [5]: (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; and R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a haloalkyl group having 1 to 20 carbon atoms; however, R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ⁸ and R ⁹ or R ¹⁰ and R ¹¹ An alkylene chain may also be formed together; A represents a divalent organic group; n represents an integer of 2 or more). The polyimine of claim 8, wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are a hydrogen atom. .