JP2002080597A - Method for producing polyimide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new method for producing a multi-branched polyimide resin. SOLUTION: This method for producing the polyimide resin is characterized in that a compound represented by formula 4 (wherein, Ar is a tetravalent organic group; R1 and R2 are same or different, and each hydrogen atom or trimethylsilyl group; R3 and R4 are same or different and each hydrogen atom a 1-10C alkyl group, an aryl group or trimethylsilyl group) is heated in the absence of a polymerization catalyst to condense the compound, and the product is optionally imidized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an interlayer insulating film for a semiconductor device, a protective film for a semiconductor device, an alignment film for a liquid crystal display, an interlayer insulating film for a multilayer printed wiring board, a wire covering material, a protective film (paint), and glass. The present invention relates to a method for producing a polyimide resin used for a fiber or carbon fiber composite material.

[0002]

2. Description of the Related Art Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protection film and an interlayer insulating film of a semiconductor element. There is a demand for remarkable improvements in heat cycle resistance and heat shock resistance due to the shift to surface mounting due to the thinning and miniaturization of packages and solder reflow, and further high performance polyimide resins are required. I have. In addition, there is a great demand for lowering the dielectric constant of the polyimide resin in order to improve the execution speed of the semiconductor element.

On the other hand, considering the workability of the polyimide resin, it is preferable that the resin is soluble in an organic solvent and the viscosity of the solution is low. However, conventional polyimide resins have no solubility in organic solvents, so they are thinned at the stage of polyamic acid, a precursor of polyimide,
The polyimide film was formed by heat treatment, and the process was complicated. In addition, even a rarely known polyimide resin soluble in an organic solvent does not always have high solubility, and the viscosity of the solution is high.

[0004]

SUMMARY OF THE INVENTION The inventors of the present invention have conducted various studies with the aim of providing a polyimide resin which is soluble in an organic solvent, has a low solution viscosity, and has high processability.
(I) The following general formulas (1), (2) and (3):

[0005]

Embedded image [In the formula, Ar represents a tetravalent organic group, ABN, CDN and efN are the same or different, unsubstituted amino group, a cyclic amide group or C _1-10 - alkyl group, an aryl group, a trimethylsilyl group, Represents a divalent hydrocarbon group having 2 to 7 chain members or an amino group substituted with a monovalent or divalent acyl group, and cdN and efN in the same repeating unit are
Linked together, the following formula (A):

[0006]

Embedded image —NH—CE—NH— (A) In the formula, CE may represent a divalent group represented by a divalent hydrocarbon group or an acyl group. ], And a polyimide resin having a repeating unit represented by the following formula:
A patent application has been filed as No. 2. In this patent application, the disclosed method for producing the polyimide resin is represented by the following general formula (4):

[0007]

Embedded image (Wherein, Ar represents a tetravalent organic group, and R ¹ and R ² are
The same or different, represents a hydrogen atom or a trimethylsilyl group, and R ³ and R ⁴ are the same or different and are a hydrogen atom,
It represents an alkyl group, an aryl group or trimethylsilyl group - C _1-10. ) In the presence of a polymerization catalyst (condensing agent) such as diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate (DBOP) and triphenyl phosphite-pyridine. By self-condensing in a solution, the following general formulas (5) and (6)
And general formula (7):

[0008]

Embedded image [Wherein, Ar represents a tetravalent organic group, R ³ represents a hydrogen atom,
C _1-10 - alkyl group, an aryl group or trimethylsilyl group, ABN, CDN and efN are the same or different, unsubstituted amino group, a cyclic amide group or C _1-10 - alkyl group, an aryl group, trimethylsilyl Group, chain member 2
7 represents an amino group substituted by a divalent hydrocarbon group or a monovalent or divalent acyl group, and cdN and efN in the same repeating unit are linked to each other to form the following formula (A):

[0009]

Embedded image In the formula, CE may represent a divalent group represented by the formula (wherein CE represents a divalent hydrocarbon group or an acyl group). And producing a multi-branched polyamic acid intermediate having a repeating unit represented by the formula (1) and heating or subjecting it to a chemical treating agent to obtain a desired multi-branched polyimide resin. An object of the present invention is to provide a method for producing a multi-branched polyimide resin different from the above-mentioned production method.

[0010]

The present invention includes the following inventions. (i) The following general formula (4):

[0011]

Embedded image (Wherein, Ar represents a tetravalent organic group, and R ¹ and R ² are
The same or different, represents a hydrogen atom or a trimethylsilyl group, and R ³ and R ⁴ are the same or different and are a hydrogen atom,
It represents an alkyl group, an aryl group or trimethylsilyl group - C _1-10. The compound of formula (I) is condensed by heating in the absence of a polymerization catalyst, and then, if necessary,
A method for producing a polyimide resin, comprising imidization. (ii) The production method according to (i), wherein the reaction temperature in the condensation reaction is 50 to 400 ° C. (iii) The polyimide resin has the following general formula (1), general formula (2) and general formula (3):

[0012]

Embedded image [In the formula, Ar represents a tetravalent organic group, ABN, CDN and efN are the same or different, unsubstituted amino group, a cyclic amide group or C _1-10 - alkyl group, an aryl group, a trimethylsilyl group, Represents a divalent hydrocarbon group having 2 to 7 chain members or an amino group substituted with a monovalent or divalent acyl group, and cdN and efN in the same repeating unit are
Linked together, the following formula (A):

[0013]

Embedded image In the formula, CE may represent a divalent group represented by the formula (wherein CE represents a divalent hydrocarbon group or an acyl group). ] The production method according to the above (i) or (ii), having a repeating unit represented by the formula: (iv) The following general formula (4):

[0014]

Embedded image (Wherein, Ar represents a tetravalent organic group, and R ¹ and R ² are
The same or different, represents a hydrogen atom or a trimethylsilyl group, and R ³ and R ⁴ are the same or different and are a hydrogen atom,
It represents an alkyl group, an aryl group or trimethylsilyl group - C _1-10. A method for producing a polyimide resin raw material, comprising condensing a compound represented by the formula (1) by heating in the absence of a polymerization catalyst.

(V) The reaction temperature in the condensation reaction is 50 to 4
The production method according to (iv), wherein the temperature is 00 ° C. (vi) A polyimide resin raw material that can be obtained by the production method described in (iv) or (v) and is soluble in an organic solvent. (vii) The polyimide resin raw material according to (vi), wherein the organic solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran. (viii) not N-acylated, N-methyl-2-
The polyimide resin raw material according to (vi), which is soluble in at least one organic solvent selected from the group consisting of pyrrolidone, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.

[0016]

BEST MODE _FOR CARRYING OUT THE INVENTION In the present specification, C _1-10 -alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-
Butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Examples include a decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group, a 1-naphthyl group,
Aromatic hydrocarbon groups such as -naphthyl group; furyl group, thienyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, An aromatic heterocyclic group such as a quinolyl group and an isoquinolyl group is exemplified. Examples of the monovalent acyl groups such as formyl group, acetyl group, propanoyl group, butanoyl group, pentanoyl group, C _1-10, such as hexanoyl - aliphatic acyl group; a benzoyl group, a substituted or unsubstituted, such as toluoyl An aroyl group;

As the divalent acyl group, a divalent substituted or unsubstituted aromatic acyl group, for example, a phthaloyl group, a naphthalene-1,2-dicarbonyl group, a naphthalene-2,3-
Dicarbonyl group; divalent substituted or unsubstituted alicyclic acyl group, for example, cyclohexane-1,2-dicarbonyl;
Examples thereof include a valent substituted or unsubstituted aliphatic acyl group such as a malonyl group, a succinyl group, and a glutaryl group. These divalent acyl groups include, for example, the aforementioned C _1-10 -alkyl group, aryl group, trimethylsilyl group, acyl group, and a C _1-10 -alkoxy group corresponding to the aforementioned C _1-10 -alkyl group, A substituted or unsubstituted aryloxy group (for example,
Phenoxy group, 3,5-bis (4-nitrophenoxy)
It may be substituted with one or more substituents selected from a phenoxy group, a halogen atom and the like.

As the divalent hydrocarbon group having 2 to 7 chain members,
An alkylene group (divalent alkyl group) having 2 to 7 chain members, such as
For example, ethylene, trimethylene, tetramethylene,
Tamethylene group, hexamethylene group; divalent of 2 to 7 chain members
Alicyclic hydrocarbon groups such as 2,3-tetramethylene
A tramethylene group; an arylene group (a divalent aryl group),
For example, 2,2'-biphenylene group; divalent aromatic ring-containing carbon
Examples include a hydride group, for example, an o-xylylene group. This
These divalent hydrocarbon groups are, for example, the aforementioned C _1-10-A
Alkyl, aryl, trimethylsilyl, acyl
And C_{1- Ten}-C corresponding to the alkyl group_1-10-Al
A oxy group, a substituted or unsubstituted aryloxy group (eg,
For example, a phenoxy group, 3,5-bis (4-nitrophenoxy)
C) one or more selected from a phenoxy group, a halogen atom, etc.
It may be substituted with the above substituent.

Examples of the cyclic amide group include a 2-oxo-1-pyrrolidinyl group and a 2-oxopiperidino group. Examples of the compound represented by the formula (4) used as a production raw material in the production method of the present invention include, for example,
The following are mentioned.

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image [Wherein, R ¹ and R ² are the same or different and represent a hydrogen atom or a trimethylsilyl group, and R ³ and R ⁴ are the same or different and represent a hydrogen atom, a C _1-10 -alkyl group, an aryl group or X represents a trimethylsilyl group, and X, Y and Z represent
Same or different, a direct bond or a linking group (eg, O,
NR (where R is a hydrogen atom or an organic group (eg, C
_1-10 -alkyl group, aryl group). ), S, S
O, SO ₂ , CO, or a divalent organic group such as a C _1-10 -alkylene group, a phenylene group, a biphenylene group, a terphenylene group, and a naphthylene group. ). ]

The tetravalent organic group represented by Ar in the above formulas (1) to (7) is obtained by converting the compound represented by the formula (4) into a substituent such as R ¹ HN, R ² HN, COOR ^3. and corresponds to minus the COOR ^4, but not limited to the specific examples described above, also, is not particularly limited bonding position. The production method of the present invention is characterized in that the compound represented by the formula (4) is condensed by heating in the absence of a polymerization catalyst, and then, if necessary, is imidized.

In the production method of the present invention, the reaction is carried out in the presence or absence of a solvent. The solvent used here is not limited as long as it does not substantially interfere with the condensation reaction.
Amide solvents such as methyl-2-pyrrolidone and N, N-dimethylacetamide, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, benzonitrile, pyridine, chloroform, dichloromethane, 1,2-dichloroethane, Examples thereof include halogen solvents such as 1,2,2-tetrachloroethane and ether solvents such as tetrahydrofuran and dioxane / diglyme. In particular, when an amide solvent such as N-methyl-2-pyrrolidone or N, N-dimethylacetamide is used, a high-polymer polyamic acid intermediate can be obtained.

The reaction temperature of the condensation reaction is usually 50 to 4
The reaction temperature is usually 00 ° C, preferably 70 to 200 ° C, and the reaction time is usually 0.2 to 48 hours, preferably 0.5 to 24 hours. This reaction is preferably performed under reduced pressure (for example, a vacuum pump or an aspirator) in the presence of an inert gas such as nitrogen gas or argon gas.

The polymer obtained by the above condensation reaction is
In some cases, imidization is not performed. In this case, the imidization reaction is performed as follows. The non-imidated polymer obtained by the present condensation reaction is generally obtained from an organic solvent such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide and tetrahydrofuran, whether or not N-acylated. It has the property of being soluble in at least one organic solvent selected from the group consisting of:

On the other hand, Japanese Patent Application No. 2000-20086
As disclosed in the specification of No. 2, the compound represented by the formula (4) is converted to (2,3-dihydro-2-thioxo-
Diphenyl 3-benzoxazolyl) phosphonate (DB
OP), a multibranched polyamic acid intermediate obtained by self-condensing in a solution in the presence of a polymerization catalyst (condensing agent) such as triphenyl phosphite-pyridine, when not N-acylated, Generally, it does not show solubility in organic solvents. The polyimide resin of the present invention can be produced by subjecting the polyimide resin raw material obtained by condensation according to the method of the present invention to heat treatment or chemical treatment.

In the heat treatment, for example, a film is directly cast from a polymerization solution of the polyimide resin raw material to form a film.
By heating to ~ 400 ° C, the polyimide resin film of the present invention can be produced. Regardless of the shape of the polyimide resin raw material, the desired polyimide resin can also be obtained by heating to 50 ° C. or higher in a solvent having a high boiling point such as cresol, chlorobenzene, diphenyl ether, nitrobenzene, or the like.

In the chemical treatment, for example, the film is directly cast from a polymerization solution of the above-mentioned polyimide resin raw material to form a film, and a target having a strong dehydrating action such as acetic anhydride, phosphorus pentoxide, or polyphosphoric acid is applied. A polyimide resin film can be manufactured. At this time, the presence of a base such as pyridine can accelerate the imidization reaction. Also, regardless of the shape of the polyimide resin raw material, dimethylformamide, benzene, toluene, diethylether, tetrahydrofuran, chloroform and the like, in a solvent that does not substantially react with a strong dehydrating agent such as acetic anhydride, acetic anhydride or the like The desired polyimide resin film can be produced by reacting a reagent having a strong dehydration effect. The reaction temperature of this imidization reaction is usually 0 to 400 ° C, preferably 20 to 200 ° C, and the reaction time is usually 0.2 to 48 hours, preferably 0.5 to 24 hours.

According to the present invention, an amino group or trimethylsilyl is used as a terminal group of the polyimide resin raw material and the polyimide resin having the repeating units represented by the general formulas (1), (2) and (3). Although an amino group is present, these can be chemically modified by a method such as alkylation (or arylation), acylation, or imidation.

Examples of these chemical modification methods include, for example, methyl iodide, propyl iodide, pentyl iodide,
Monoalkylation with octyl bromide, etc .; Cycloalkylation with 1,4-dibromobutane, 1,5-dibromopentane, etc .; with acetyl chloride, pentanoyl chloride, heptanoyl chloride (enantyl chloride), decanoyl chloride, etc. Acylation; lactamization with γ-butyrolactone or the like; succinic anhydride, glutaric anhydride,
Examples include imidization with maleic anhydride, phthalic anhydride, 3-methylphthalic anhydride, 4-methylphthalic anhydride, and the like.

In the production of the polyimide resin according to the present invention, not only the production raw material represented by the above formula (4) is used alone to produce a multi-branched polyimide resin, but also the production of a conventionally used linear polyimide. It can be used by mixing with raw materials. At this time, from the beginning of the production, the production raw material represented by the formula (4) and the conventionally used production raw material of the linear polyimide can be mixed and reacted. Further, the polyimide resin raw material and the conventionally used raw material for producing linear polyimide can be mixed and reacted. Conventionally used raw materials for producing a linear polyimide include the following tetracarboxylic dianhydrides, tetracarboxylic diesters and acid chlorides thereof, and diamine compounds which react with them.

[0033]

Embedded image (In the formula, R represents a hydrogen atom, a C _1-10 -alkyl group or an aryl group.) In the polyimide resin obtained by the present invention, the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) Of the number of repeating units represented by general formula (1), the number of repeating units represented by general formula (2) and the number of repeating units represented by general formula (3) A certain degree of branching is preferably 0.05 to 0.9.
5, more preferably 0.2 to 0.9.

The solubility of the polyimide resin obtained according to the present invention in an organic solvent is dimethyl sulfoxide, N-
For 1 L of an organic solvent such as methyl-2-pyrrolidone, N, N-dimethylacetamide and dimethylformamide,
Preferably 1 g to 1000 g, more preferably 10 g
To 100 g.

The intrinsic viscosity (η _inh ) of the polyimide resin obtained according to the present invention is 0.5 g / dL of N-methyl-
In 2-pyrrolidone at 30 ° C., preferably 0.01 to
1.5 dL / g, more preferably 0.05 to 0.7 dL
/ G. The weight average molecular weight of the polyimide resin obtained by the present invention is preferably 1000 to 500000,
It is more preferably 3,000 to 100,000, and the degree of polymerization is preferably 3 to 2,000, more preferably 10 to 4
00.

[0036]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples and Examples, but the scope of the present invention is not limited to these Examples. (1) Reagents Dimethyl sulfoxide (DMSO), N-methyl-2-
Pyrrolidone (NMP), dimethylformamide (DM
F), pyridine and triethylamine were distilled and used in the presence of calcium hydride, dichloromethane was calcium chloride, acetic anhydride was magnesium, and acetyl chloride was phosphorus pentachloride. As other reagents, commercial products were used for the reaction as they were.

(2) Measuring device The infrared absorption spectrum was measured by Shimadzu FT / IR-810.
It was measured with a zero Fourier transform infrared spectrophotometer. ¹ H-
The NMR spectrum was obtained from JEOL JNM-AL300 (30
0 MHz) was measured by an NMR spectrometer.
Thermogravimetric analysis and differential scanning calorimetry were measured by Seiko Instruments TG / DTA6200 and DSC6200. The number-average molecular weight and weight-average molecular weight are determined by gel permeation chromatography (GPC) equipped with a light scattering detector (Wyatt Technology Co. mini DAWN) and a differential refractive index detector (Shodex RI-71) in terms of absolute molecular weight or polystyrene conversion. (Pump: JASCO HPLC880P
U, column: polystyrene-divinylbenzene column Sh
Two odex KD 806M and one KD 802, developing solution: 0.01m
ol / L of lithium bromide dissolved in DMF). dn /
dc is 690 by Wyatt Technology Co. Optilab 903
The measurement was performed using a laser beam of nm.

[Production Example 1] Synthesis of 3,5-bis (4-aminophenoxy) diphenyl ether-3 ', 4'-dicarboxylic acid monomethyl ester 6 (part 1) (formula 1)

[0039]

Embedded image

(1) Sodium methoxide in a 300 ml three-necked flask equipped with 1 dropping funnel of sodium-3,5-dimethoxyphenoxide and a nitrogen inlet tube under a nitrogen atmosphere.
After adding 479 g (64.4 mmol), under ice bath,
40 ml of methanol was added dropwise. After sodium methoxide was completely dissolved, 9.928 g of 3,5-dimethoxyphenol (64.4) dissolved in 40 ml of methanol was used.
mmol) was added dropwise. After the dropwise addition, the mixture was stirred in an ice bath for 20 minutes and at room temperature for 1 hour, concentrated to dryness by an evaporator, and dried overnight at 80 ° C. under reduced pressure. Sodium-3,5-dimethoxyphenoxide 1 as pale yellow powder11.
287 g (99% yield) were obtained.

[0041] (2) 4- (3,5-dimethoxy-phenoxy) in 1000ml round-bottomed flask equipped with a phthalonitrile 2 nitrogen inlet tube, wherein (1) sodium-3,5-dimethoxy phenoxide obtained in 7.531g (42.8 mmol),
7.401 g of 4-nitrophthalonitrile (42.8 mm
ol) and 160 ml of DMSO, and the mixture was reacted at room temperature under a nitrogen atmosphere for 1 hour.
After collecting the formed precipitate by filtration, 1.2N
It was sufficiently washed with hydrochloric acid. After drying overnight at 80 ° C. under reduced pressure, 10.870 g of 4- (3,5-dimethoxyphenoxy) phthalonitrile 2 as a yellow powder (91% yield, melting point 131-
135 ° C).

FIG. 1 shows the infrared absorption spectrum (KBr).
^{The 1} H-NMR spectrum (DMSO-d ₆ ) is shown in FIG. Elemental analysis value (C ₁₆ H ₁₂ N ₂ O ₃ ) Calculated value C: 6
8.57, H: 4.32, N: 9.99. Experimental value
C: 68.40, H: 4.53, N: 10.01.

(3) 4- (3,5-Dimethoxyphenoxy) phthalic acid 3 The 4- (3) obtained in (2) above was placed in a 500 ml eggplant flask equipped with a nitrogen inlet tube, a reflux condenser and a dilute hydrochloric acid trap. , 5-Dimethoxyphenoxy) phthalonitrile 10.000 g (35.7 mmol), distilled water 50 ml
15g of potassium hydroxide (267.3 mmol) dissolved in
l) and after adding 100 ml of ethylene glycol, 3
Heated to reflux for hours. After cooling, the reaction solution was poured into 400 ml of distilled water, and concentrated hydrochloric acid was added until the solution became acidic.
The resulting precipitate was collected by filtration and thoroughly washed with 1.2N hydrochloric acid. After drying overnight at room temperature under reduced pressure, 4-yellow powder
(3,5-dimethoxy-phenoxy) phthalic acid 3 10.
527 g (93% yield) were obtained.

FIG. 3 shows the infrared absorption spectrum (KBr).
FIG. 4 shows the ¹ H-NMR spectrum (DMSO-d ₆ ). Elemental analysis value (C ₁₆ H ₁₄ O ₇ ) Calculated value C: 60.
38, H: 4.43. Experimental values C: 60.09, H:
4.50.

(4) 3,5-bis (4-nitrophenoxy) diphenyl ether-3 ', 4'-dicarboxylic anhydride 4 (a) 1000 ml equipped with a dropping funnel and a nitrogen inlet tube
In the eggplant flask, 4- (3,5) obtained in the above (3) was added.
-Dimethoxyphenoxy) phthalic acid 16.960 g (5
8.4 mmol) and 330 ml of dichloromethane, and then 75 g of boron tribromide (29
9 mmol) was added dropwise. After the dropwise addition, the mixture was reacted for 1 hour in an ice bath and for 20 hours at room temperature.
And extracted with 2800 ml of diethyl ether. 0.6 N of the recovered diethyl ether extract
The extract was washed with 3800 ml of hydrochloric acid, dehydrated with anhydrous magnesium sulfate, and concentrated to dryness with an evaporator. After drying at room temperature under reduced pressure overnight, 12.780 g of an orange viscous product was obtained.

(B) In a 500 ml three-necked flask equipped with a nitrogen inlet tube and a reflux condenser, 40.690 g (267.9 mmol) of cesium fluoride was added under a nitrogen stream and dried with a heat gun. 12.780 g of the orange product obtained in the above, 4-fluoronitrobenzene 1
0.10 ml (95.9 mmol) and DMSO 19
After adding 0 ml and reacting at 115 ° C. for 24 hours, the reaction solution was poured into 2000 ml of ice water. The resulting precipitate was collected by filtration and thoroughly washed with distilled water. After drying overnight at room temperature under reduced pressure, 25.020 g of a product as a pale yellow powder was obtained.

(C) In a 500 ml eggplant flask equipped with a nitrogen inlet tube and a reflux condenser, under a nitrogen atmosphere, 25.020 g of the pale yellow powder product obtained above and acetic anhydride 2
0 ml and 260 ml of glacial acetic acid were added, and the mixture was heated under reflux for 2 hours. 20 minutes after the start of reflux, an orange precipitate was observed in the reaction system. After standing to cool, the precipitate was collected by filtration and washed sufficiently with acetic anhydride and glacial acetic acid. After drying overnight at 130 ° C. under reduced pressure, pale yellow powder of 3,5-bis (4-nitrophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic anhydride 4
16.132 g (yield 59%, melting point 202-207 ° C)
I got

FIG. 5 shows the infrared absorption spectrum (KBr). Elemental analysis value (C ₂₆ H ₁₄ N ₂ O ₁₀ ) Calculated value C:
60.71, H: 2.74, N: 5.45. Experimental value
C: 60.66, H: 2.82, N: 5.39.

(5) 3,5-bis (4-nitrophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic acid monomethyl ester isomer mixture 5 In a 200 ml eggplant flask equipped with a nitrogen inlet tube,
10.042 g (19.5 mmol) of 3,5-bis (4-nitrophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic anhydride obtained in the above (4) and hydroxylation dissolved in 100 ml of special-grade methanol Potassium 1.
7 g (30.3 mmol) was added and reacted at room temperature for 5 hours under a nitrogen atmosphere. Three hours after the start of the reaction, a uniform reaction solution was obtained. After the completion of the reaction, the reaction solution was filtered, and the obtained filtrate was poured into 1500 ml of 0.6N hydrochloric acid. The resulting precipitate was collected by filtration, sufficiently washed with 0.6N hydrochloric acid, and dried at room temperature under reduced pressure overnight to obtain a pale yellow powder product. This was redissolved in a potassium hydroxide-methanol solution of the same concentration as above, reprecipitated with 0.6N hydrochloric acid, dried, and then pale yellow powdered 3,5-bis (4-nitrophenoxy) diphenyl ether-3 ′ to give 4'-dicarboxylic acid monomethyl ester isomeric mixture 5 9.770G (92% yield). The isomer mixture ratio of the para-: meta-monomethyl ester substituted product determined by ¹ H-NMR spectrum analysis was 21:
79.

FIG. 6 shows the infrared absorption spectrum (KBr).
FIG. 7 shows the ¹ H-NMR spectrum (DMSO-d ₆ ). Elemental analysis (C ₂₇ H ₁₈ N ₂ O ₁₁ ) Calculated C:
59.35, H: 3.32, N: 5.13. Experimental value
C: 58.80, H: 3.32, N: 5.02. (6) 3,5-bis (4-aminophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic acid monomethyl ester 6 In a 90 ml autoclave, the 3,5-bis (4-nitrophenoxy) obtained in the above (5) was placed. ) Diphenyl ether-3 ′, 4′-dicarboxylic acid monomethyl ester isomer mixture 3.020 g (5.5 mmol), 10% palladium on activated carbon 0.3060 g and special grade methanol 30
Then, the mixture was stirred at room temperature under hydrogen pressure. After the hydrogen absorption reached saturation, the reaction was carried out under a hydrogen atmosphere of 8 atm for 48 hours. After completion of the reaction, the mixture was treated with Celite, and the obtained methanol solution was concentrated to dryness using an evaporator.
It was dried at 45 ° C. under reduced pressure for 100 hours to obtain Compound 6 as a brown powder. The yield was 2.308 g (86% yield). Para determined from ¹ H-NMR spectrum analysis:
The isomer mixture ratio of the substituted meta-monomethyl ester is 2
1:79.

The infrared absorption spectrum (KBr) is shown in FIG.
FIG. 9 shows the ¹ H-NMR spectrum (DMSO-d ₆ ). Elemental analysis value (C ₂₇ H ₂₂ N ₂ O ₇ ) Calculated value C: 6
6.66, H: 4.56, N: 5.76. Experimental value
C: 66.12, H: 4.56, N: 5.61.

[Production Example 2] Synthesis of 3,5-bis (4-aminophenoxy) diphenyl ether-3 ', 4'-dicarboxylic acid monomethyl ester 6 (part 2) (formula 2)

[0053]

Embedded image

(1) 3,5-dihydroxyphenyl-3
', In a flask and dried 4'-dicyano phenyl ether 2', 1,3,5-benzenetricarboxylic ol (phloroglucinol) 2.52 g (20 mmol)
And 2.786 g of 4-nitrophthalonitrile (16 mo
l) was dissolved in 50 ml of DMF and potassium carbonate was added.
28 g (60 mol) were added. Put the solution under nitrogen atmosphere
After heating at room temperature for 8 hours, the mixture was poured into 1000 ml of water, and the resulting precipitate was filtered off. 1 until the filtrate reaches pH 3
An 8% aqueous hydrochloric acid solution was added, and the resulting precipitate was filtered off. The obtained solid was recrystallized from a mixed solution of water / methanol = 80/20 (volume ratio) to obtain 1.21 g of a pure product. The yield was 24%. FIG. 10 shows an NMR spectrum and FIG. 13 shows an infrared absorption spectrum.

(2) 3,5-dihydroxyphenyl-3
', 4'-dicarboxyphenyl ether 2 "compound 2'0.5 g of potassium hydroxide 2.11 g 5
The mixture was refluxed under heating for 4 hours in ml of water. After cooling to room temperature, an 18% aqueous hydrochloric acid solution was added to the solution until the pH reached 4, and water was distilled off using an evaporator.
ml of acetone was added. After the generated precipitate was separated by filtration, acetone was distilled off from the filtrate and dried at 60 ° C. under reduced pressure to obtain 0.46 g of a yellow solid. The yield was 80%. FIG. 11 shows the NMR spectrum and FIG. 14 shows the infrared absorption spectrum.

(3) 3,5-bis (4-nitrophenoxy) diphenyl ether- 3 ' , 4'-dicarboxylic acid 3
' Compound 2' 0.1 g (0.345 mmol), p-fluoronitrobenzene 0.0972 g (0.069 mm
ol) and 0.27 g (2 mmol) of potassium carbonate in 1.
Dissolved in 5 ml DMF. The solution was heated and stirred at 115 ° C. for 24 hours, and the solution was poured into 100 ml of a 1M aqueous hydrochloric acid solution, and the formed precipitate was separated by filtration. After washing with water and drying at 80 ° C. under reduced pressure, 0.16 g of a yellow solid was obtained. The yield was 87%. FIG. 12 shows an NMR spectrum and FIG. 15 shows an infrared absorption spectrum. Hereinafter, (4) and (c) of Production Example 1
To (6) to give 3,5-bis (4-aminophenoxy) diphenyl ether-3 ′,
4′-dicarboxylic acid monomethyl ester 6 can be produced.

Reference Example 1 Synthesis of Polymer 7 (Formula 3)

[0058]

Embedded image

[0059] During 50ml three-necked flask equipped with a nitrogen inlet tube, Production Example 1 (6) obtained in Compound 6 0.
603 g (1.24 mmol), (2,3-dihydro-
0.568 g (1.48 mmol) of diphenyl 2-thioxo-3-benzoxazolyl) phosphonate (DBOP)
l), 0.17 ml of triethylamine (1.24 mmol
l) and 3 ml of NMP were added and reacted at room temperature for 3 hours under a nitrogen stream. After completion of the reaction, 6 ml of NMP was added to the reaction solution for dilution, and then methanol (0.1 wt% LiCl / CH ₃ OH) in which 0.1 wt% of lithium chloride was dissolved.
The polymer was poured into 350 ml to precipitate the polymer. After collecting by filtration and drying overnight at room temperature under reduced pressure, a white powder of polymer 7 was obtained. The yield was 0.504 g (86% yield). Table 1 shows the solubility in organic solvents.

Reference Example 2 Polymer8(Formula 3) After polymerizing for 3 hours in Reference Example 1 (Step a of Formula 3),
Equipped with a funnel and dissolved in 6 ml of NMP under an ice bath
2.80 ml (39.4 mmol) of acetyl chloride is added dropwise.
did. After dropping, react for 30 minutes in an ice bath and 3 hours at room temperature
I let it. After completion of the reaction, add 20 ml of NMP to the reaction solution.
After dilution, 0.1 wt% LiCl / CH₃OH200
The solution was added to 0 ml to precipitate the polymer. After collection by filtration, D
Redissolved in MF, 0.1 wt% LiCl / CH₃OH
Re-precipitation treatment and drying8Get
Was. The yield was 0.506 g (80% yield). GP
Weight average molecular weight (M_w) Is 7000
0, the molecular weight distribution (M_w/ M _n) Was 2.1 (d
n / dc is 0.152 mL / g). Intrinsic viscosity
(Η_{in h}) At 30 ° C. in 0.5 g / dL NMP
It was 0.23 dL / g. Solubility in organic solvents
It is shown in Table 1.

Reference Example 3 Synthesis of Polymer 9 (Formula 3) 0.104 g (0.2%) of polymer 7 obtained in Reference Example 1
2 mmol) was placed on a petri dish and heated under reduced pressure at 300 ° C. for 1 hour. Polymer 9 was obtained as a yellow powder. The yield was 0.095 g (98% yield). Under a nitrogen atmosphere, the 10% thermal weight loss temperature (T ₁₀ ) was 555 ° C.
Table 1 shows the solubility in organic solvents.

Reference Example 4 Synthesis of Polymer 10 (Formula 3) The polymer 7 obtained in Reference Example 1 was placed in a 50 ml three-necked flask equipped with a nitrogen inlet tube and a reflux condenser.
3 g (0.96 mmol), 1.10 ml of acetic anhydride (1
1.70 mmol), 0.70 ml of pyridine (8.70 mmol)
mmol) and 7 ml of DMSO.
The reaction was performed at 100 ° C. for 24 hours. After the reaction was completed, 20 ml of DMSO was added to the reaction solution to dilute it, and then 0.1 wt%
The polymer was poured into 1800 ml of LiCl / CH ₃ OH to precipitate the polymer. After being collected by filtration, redissolved in DMF,
After re-precipitation treatment with wt% LiCl / CH ₃ OH, the mixture was heated to 0.
It was washed with 1wt% LiCl / _CH 3 OH. After recovery, the polymer was dried overnight at 80 ° C. under reduced pressure to obtain a pale yellow powder of Polymer 10 . The yield was 0.398 g (86% yield). G
M _w determined by PC measurement was 1880000, and M _w /
_Mn was 3.0 (dn / dc was 0.168 mL /
g). η _inh is 30 ° C. in 0.5 g / dL NMP.
Was 0.29 dL / g. _{T 10} is 470 ° C. under a nitrogen atmosphere, a glass transition temperature _{(T g)} was 193 ° C.. ^The degree of branching (D) determined from ¹ H-NMR spectrum analysis
B) was 0.48. Table 1 shows the solubility in organic solvents. It is soluble in NMP even at a concentration of 200 mg / mL at room temperature, and 4
It was found that it was soluble even at a concentration of 00 mg / mL. Elemental analysis value (C ₂₈ H ₁₈ N ₂ O ₆ ) Calculated value C: 7
0.28, H: 3.79, N: 5.85. Experimental value
C: 67.74, H: 3.53, N: 5.55.

[Reference Example 5] Polymer11(Formula 3) 50 ml three-neck filter equipped with a nitrogen inlet tube and a reflux condenser
In Lasco, the polymer obtained in Reference Example 28 0.15
0 g (0.29 mmol), 0.36 ml of acetic anhydride
(3.90 mmol), 0.24 ml of pyridine (3.0
mmol) and 3 ml of DMSO.
The reaction was performed at 100 ° C. for 24 hours. After the reaction is completed, the reaction solution
Was diluted with 9 ml of DMSO, and then 0.1 wt% L
iCl / CH ₃OH into 800 ml to precipitate the polymer.
I let you go. After collecting by filtration, redissolve in DMF and add 0.1w
t% LiCl / CH₃After reprecipitation treatment with OH, heat 0.1
wt% LiCl / CH₃Washed with OH. After collection, decompression
After drying at 80 ° C overnight, light yellow powder polymer11Get
Was. The yield was 0.113 g (80% yield). GP
M obtained by C measurement_wIs 37000 and M_w/ M_nIs
1.6 (dn / dc: 0.168 mL / g).
η_inhIs 0.1% at 30 ° C. in 0.5 g / dL NMP.
It was 16 dL / g. T under nitrogen atmosphere₁₀Is 490
° C, T_gWas 189 ° C.¹H-NMR spectrum
The DB determined from the analysis was 0.49. For organic solvents
The solubility is shown in Table 1. 200 mg at room temperature
/ ML, it is soluble in NMP and 100
Can be soluble at 400 ° C even at a concentration of 400 mg / mL.
I understood. Elemental analysis value (C₂₈H₁₈N₂O₆) Calculated value C: 7
0.28, H: 3.79, N: 5.85. Experimental value
C: 68.24, H: 3.60, N: 5.66.

Reference Example 6

Embedded image

The polyimide 12 represented by the formula (4) (M _w = 7
7000, _Mw / _Mn = 1.7 (in terms of polystyrene),
η _inh = 0.34 dL / g (0.5 g / dL NMP
) At room temperature and at 1
At 00 ° C., it was soluble up to a concentration of 170 mg / mL, but only partially dissolved at a concentration of 200 mg / mL.

[0066]

[Table 1]

Example 1 Synthesis of Polymer 13 (Formula 5)

[0068]

Embedded image

[0069] During 50ml three-necked flask equipped with a nitrogen inlet tube, Production Example 1 (6) obtained in Compound 6 0.
202 g (0.42 mmol) and 2 ml of NMP were added and reacted at 100 ° C. for 24 hours under a nitrogen stream. During the reaction, precipitation of insolubles was observed in the reaction mixture. After completion of the reaction, the reaction mixture was poured into methanol to precipitate a polymer. After filtration, DMF was added to the residue, separated into a soluble part and an insoluble part, and the soluble part was again subjected to precipitation treatment with methanol and dried under reduced pressure at room temperature overnight to obtain a white powder of polymer 13. I got The yield was 0.127 g. The intrinsic viscosity (η _inh ) is 30 ° C. in 0.5 g / dL NMP.
Was 0.20 dL / g. Infrared absorption spectrum (KBr) is shown in FIG. 16, ¹ H-NMR spectrum (DMS
Od ₆ , 100 ° C.) is shown in FIG.

Example 2 Synthesis of Polymer 14 (Equation 5) 0.013 g of the polymer 13 obtained in Example 1 was weighed into a sample bottle, and was weighed at 200 ° C. for 1 hour, 250 ° C. for 1 hour, and under reduced pressure. To give Polymer 14 as a yellow powder. The yield was 0.013 g. T under nitrogen atmosphere
₁₀ was 540 ° C. Infrared absorption spectrum (KB
r) is shown in FIG.

Example 3 PolymerFifteen(Formula 5) 50 ml three-neck filter equipped with a nitrogen inlet tube and a reflux condenser
In Lasco, the polymer obtained in Example 113 0.1
82 g, acetic anhydride 0.44 ml, pyridine 0.28 ml
And 2.80 ml of DMF, and the mixture was heated at 120 ° C.
For 24 hours. After completion of the reaction, the reaction mixture was
600 ml of methanol water containing 12% hydrochloric acid (vol%)
Into the solution (50:50 vol) to precipitate the polymer
I let you. After collecting by filtration, drying at 80 ° C under reduced pressure overnight, pale yellow
Powder polymerFifteenI got The yield was 0.192 g.
Was. M in absolute molecular weight determined by GPC measurement_wIs 71
000, M_w/ M_nWas 1.1 (dn / dc is
0.168 mL / g). η _inhIs 0.5 g / dL
0.14 dL / g at 30 ° C. in NMP. Nitrogen atmosphere
T under ambient atmosphere₁₀Is 435 ° C. and the glass transition temperature (T_g) Is
174 ° C. ¹H-NMR spectrum analysis
The degree of branching (DB) was 0.53. Infrared absorption
FIG. 19 shows the spectrum (KBr).¹H-NMR spectrum
(DMSO-d₆, 100 ° C.) is shown in FIG.

Example 4 Synthesis of Polymer 16 (Formula 5) 0.086 g of the compound 6 obtained in Production Example 1 (6)
(0.18 mmol) was weighed into a sample bottle and heat-treated at 100 ° C. for 1 hour under reduced pressure to obtain a brown powdered polymer 16 . The yield was 0.084 g. FIG. 21 shows the infrared absorption spectrum (KBr).

Example 5 Synthesis of Polymer 17 (Formula 5) 0.080 g of compound 6 obtained in Production Example 1 (6)
(0.16 mmol) was weighed into a sample bottle, and heated at 200 ° C. for 1 hour under reduced pressure to obtain a yellow powder polymer.
17 was obtained. The yield was 0.072 g. FIG. 22 shows the infrared absorption spectrum (KBr).

Example 6 Synthesis of Polymer 18 (Formula 5) 0.083 g of the compound 6 obtained in Production Example 1 (6)
(0.17 mmol) was weighed into a sample bottle, and heat-treated at 300 ° C. for 1 hour under reduced pressure to obtain an orange powder polymer.
18 was obtained. The yield was 0.071 g. FIG. 23 shows the infrared absorption spectrum (KBr).

[Test Example] Polymer Solubility Test Table 2 shows the results of the solubility tests (50 mg / mL) of the polymers 13 to 18 obtained in the above Examples in various organic solvents.
It was shown to.

[0076]

[Table 2]

[0077]

According to the present invention, a novel method for producing a hyperbranched polyimide resin can be provided.

[Brief description of the drawings]

FIG. 1 is a view showing an infrared absorption spectrum of 4- (3,5-dimethoxyphenoxy) phthalonitrile.

FIG. 2 shows a ¹ H-NMR spectrum of 4- (3,5-dimethoxyphenoxy) phthalonitrile.

FIG. 3 is a view showing an infrared absorption spectrum of 4- (3,5-dimethoxyphenoxy) phthalic acid.

FIG. 4 shows a ¹ H-NMR spectrum of 4- (3,5-dimethoxyphenoxy) phthalic acid.

FIG. 5 is a view showing an infrared absorption spectrum of 3,5-bis (4-nitrophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic anhydride.

FIG. 6 is a diagram showing an infrared absorption spectrum of a mixture of 3,5-bis (4-nitrophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic acid monomethyl ester isomers.

FIG. 7 is a diagram showing a ¹ H-NMR spectrum of 3,5-bis (4-nitrophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic acid monomethyl ester isomer mixture.

FIG. 8 is a view showing an infrared absorption spectrum of 3,5-bis (4-aminophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic acid monomethyl ester.

FIG. 9 is a diagram showing a ¹ H-NMR spectrum of 3,5-bis (4-aminophenoxy) diphenyl ether-3 ′, 4′-dicarboxylic acid monomethyl ester.

FIG. 10: 3,5-dihydroxyphenyl-3 ′, 4 ′
- is a chart showing ¹ H-NMR spectrum of dicyanophenyl ether 2'.

FIG. 11 shows 3,5-dihydroxyphenyl-3 ′, 4 ′
FIG. 3 is a view showing a ¹ H-NMR spectrum of -dicarboxyphenyl ether 2 ″ .

FIG. 12 shows ¹ H of 3,5-bis (4-nitrophenoxy) diphenyl ether- 3 ′, 4′-dicarboxylic acid 3 ′
It is a figure which shows -NMR spectrum.

FIG. 13 shows 3,5-dihydroxyphenyl-3 ′, 4 ′
- is a diagram showing the infrared absorption spectrum of dicyanophenyl ether 2'.

FIG. 14: 3,5-dihydroxyphenyl-3 ′, 4 ′
FIG. 3 is a view showing an infrared absorption spectrum of -dicarboxyphenyl ether 2 ″ .

FIG. 15 is a view showing an infrared absorption spectrum of 3,5-bis (4-nitrophenoxy) diphenyl ether- 3 ′, 4′-dicarboxylic acid 3 ′.

FIG. 16 is a diagram showing an infrared absorption spectrum of polymer 13 .

17 is a chart showing ¹ H-NMR spectrum of a polymer 13. FIG.

FIG. 18 is a diagram showing an infrared absorption spectrum of polymer 14 .

FIG. 19 is a diagram showing an infrared absorption spectrum of polymer 15 .

FIG. 20 is a chart showing a ¹ H-NMR spectrum of a polymer 15 .

21 shows an infrared absorption spectrum of polymer 16. FIG.

FIG. 22 is a diagram showing an infrared absorption spectrum of polymer 17 .

FIG. 23 is a diagram showing an infrared absorption spectrum of polymer 18 .

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhiro Yamanaka 2-12-1 Ookayama, Meguro-ku, Tokyo F-term in Tokyo Institute of Technology 4J043 PA02 QB05 QB33 RA34 SA06 TA32 UA121 UA131 UA141 UA261 UB011 UB151 UB281 UB291 UB301

Claims (8)

[Claims] 1. The following general formula (4): (Wherein, Ar represents a tetravalent organic group, and R ¹ and R ² are
The same or different, represents a hydrogen atom or a trimethylsilyl group, and R ³ and R ⁴ are the same or different and are a hydrogen atom,
It represents an alkyl group, an aryl group or trimethylsilyl group - C _1-10. The compound of formula (I) is condensed by heating in the absence of a polymerization catalyst, and then, if necessary,
A method for producing a polyimide resin, comprising imidization. 2. The reaction temperature in the condensation reaction is 50 to 40.
The method according to claim 1, wherein the temperature is 0 ° C. 3. A polyimide resin represented by the following general formula (1):
General formula (2) and general formula (3): [In the formula, Ar represents a tetravalent organic group, ABN, CDN and efN are the same or different, unsubstituted amino group, a cyclic amide group or C _1-10 - alkyl group, an aryl group, a trimethylsilyl group, Represents a divalent hydrocarbon group having 2 to 7 chain members or an amino group substituted with a monovalent or divalent acyl group, and cdN and efN in the same repeating unit are
Linked to each other to form a divalent compound represented by the following formula (A): -NH-CE-NH- (A) (wherein CE represents a divalent hydrocarbon group or an acyl group) May represent a group. The production method according to claim 1 or 2, which has a repeating unit represented by the formula: 4. The following general formula (4): (Wherein, Ar represents a tetravalent organic group, and R ¹ and R ² are
The same or different, represents a hydrogen atom or a trimethylsilyl group, and R ³ and R ⁴ are the same or different and are a hydrogen atom,
It represents an alkyl group, an aryl group or trimethylsilyl group - C _1-10. A method for producing a polyimide resin raw material, which comprises condensing a compound represented by the formula (1) by heating in the absence of a polymerization catalyst. 5. The reaction temperature in the condensation reaction is 50 to 40.
The method according to claim 4, wherein the temperature is 0 ° C. 6. A polyimide resin raw material which can be obtained by the production method according to claim 4 and is soluble in an organic solvent. 7. The polyimide resin raw material according to claim 6, wherein the organic solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide and tetrahydrofuran. 8. The method according to claim 6, wherein the compound is not N-acylated and is soluble in at least one organic solvent selected from the group consisting of N-methyl-2-pyrrolidone, dimethylformamide, dimethylsulfoxide and tetrahydrofuran. Of polyimide resin.