JP2001253870A - Method for producing imide compound and its new derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an imide compound useful in various fields required to have heat resistance, electric characteristics and mechanical characteristics. SOLUTION: This method for producing an imide compound comprises carrying out a reaction in the presence of 9,10-dihydro-oxa-10-phosphaphenanthrene-10- oxide in a mixed solvent of an aromatic solvent having -8.5 to 9.5 solubility parameter and a polar solvent having 9.0 to 12.1 solubility parameter at 130-160 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an imide compound which can be used in various fields where heat resistance, electrical properties and mechanical properties are required.

[0002]

2. Description of the Related Art Hitherto, as a method for producing an imide compound, a carboxylic acid anhydride and an amino compound have been used
A method in which the reaction is carried out at a temperature of from -400C has been adopted. Further, as another method, a method of performing a dehydration reaction in pyridine, dimethylacetamide, or phenol has been proposed.

[0003]

However, according to these methods, it is known that the reaction is remarkably slowed at 180 ° C. or less, and a method for producing a high-quality imide compound at 180 ° C. or less in a short time is known. Establishing it has become a major challenge for deployment in various applications.

[0004] In addition, urethane-based, epoxy-based, polyether-based and polyester-based photocurable materials have been used.
Generally known. However, these materials have a heat resistance temperature of about 200 ° C., and materials having better heat resistance are required. Specifically, higher thermal stability is required for a photoresist material for an electronic material or an interlayer insulating film. Further, a material having excellent solubility in handling is also required.

[0005]

According to the present invention, there is provided a method of formula (1):

[0006]

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Wherein R ₁ represents an aliphatic group, an alicyclic group or an aromatic group, and a carboxylic acid monoanhydride represented by the formula (2):

[0008]

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Wherein R ₂ represents an aliphatic group, an alicyclic group or an aromatic group; A represents a carboxyl group, a hydroxyl group, a mercapto group, a cyano group, a C ₁ -C ₄ linear or A carboxylic acid ester group having a branched alkyl group, a methoxy group, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ or a halogen atom; n is an integer of 0 to 4) Reacting the compound with a compound of formula (3):

[0010]

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Wherein R ₁ , R ₂ , A, and n are as defined above, wherein the 9,10-dihydro-oxa-0-phosphaphenanthrene In the presence of -10-oxide, 130 in a mixed solvent of an aromatic solvent having a solubility parameter of 8.5 to 9.5 and a polar solvent having a solubility parameter of 9.0 to 12.1
To 160 ° C.

Further, the present invention provides a method of formula (4):

[0013]

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Wherein R ₁ is as defined above, and a carboxylic acid dianhydride represented by the formula (2):

[0015]

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Wherein R ₂ , A and n are as defined above, and reacting with an amino compound represented by the formula (5):

[0017]

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(Wherein R ₁ , R ₂ , A and n are as defined above), wherein 9,10-dihydro-oxa-10-phosphaphenanthrene In a mixed solvent of an aromatic solvent having a solubility parameter of 8.5 to 9.5 and a polar solvent having a solubility parameter of 9.0 to 12.1 in the presence of -10-oxide, 13
A method characterized by reacting at 0 to 160 ° C.

Further, the present invention provides a compound of the formula (6):

[0020]

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(Wherein R ₁ is as defined above; m
Represents 1 to 10) and a carboxylic anhydride copolymer represented by the formula (2):

[0022]

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Wherein R ₂ , A and n are as defined above, and reacting with an amino compound represented by the formula (7):

[0024]

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Wherein R ₁ , R ₂ , A, n, and m are as defined above, wherein the 9,10-dihydro-oxa-10-phosphafe In the presence of nanthrene-10-oxide, in a mixed solvent of an aromatic solvent having a solubility parameter of 8.5 to 9.5 and a polar solvent having a solubility parameter of 9.0 to 12.1,
The present invention relates to a method characterized by reacting at 130 to 160 ° C.

Further, the present invention relates to the following formula (8):

[0027]

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Wherein R ₁ , R ₂ and A are as described above; p is an integer of 0 to 3; and R ₃ represents hydrogen or a methyl group. .

Further, the present invention provides a compound of the formula (9):

[0030]

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Wherein R ₁ , R ₂ , A, p and R ₃ are as defined above.

Further, the present invention provides a method of formula (10):

[0033]

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(Wherein R ₁ , R ₂ , A, m, p and R ₃ are
As described above).

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for producing an imide compound according to the present invention will be described. First, the meanings of terms will be described.

The "aliphatic group", "alicyclic group" and "aromatic group" relating to R ₁ and R ₂ are not particularly limited. Preferably, it is an aliphatic group having 2 to 39 carbon atoms, an alicyclic group having 4 to 39 carbon atoms and an aromatic group. Formulas (1) and (4) containing such “aliphatic group”, “alicyclic group” and “aromatic group”
And examples of the carboxylic anhydride of the formula (6) include aliphatic dicarboxylic anhydride and tetracarboxylic anhydride having 2 to 39 carbon atoms, and alicyclic and aromatic dicarboxylic anhydrides having 4 to 39 carbon atoms. And a tetracarboxylic anhydride, and a copolymer of an olefin having 2 to 39 carbon atoms and an unsaturated dicarboxylic anhydride. Specifically, phthalic anhydride, hymic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, methylcyclohexene 1,2,3-tricarboxylic acid 1,2 anhydride, naphthalic anhydride, pyromellitic anhydride, diphenylethertetracarboxylic anhydride, benzophenonetetracarboxylic anhydride, maleated cyclohexenetetracarboxylic anhydride, cyclobutanetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-(1,4-phenylenedioxy)
Phthalic anhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, tetralin dianhydride, perylene tetracarboxy dianhydride, 1,4-difluoro-2,3,5,6- Benzenetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, bicyclo (2.2.
1) heptanetetracarboxylic dianhydride, bicyclo (2.2.2) oct-7ene 2,3,5,6-tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, diphenylsulfonetetracarboxylic dianhydride Anhydrous,
Styrene maleic anhydride copolymer, isobutylene maleic anhydride copolymer, ethylene maleic anhydride copolymer,
Examples thereof include diisobutylene maleic anhydride copolymer, maleic acid polymer, and itaconic acid polymer.

The amino compound of the formula (2) containing such an “aliphatic group”, “alicyclic group” and “aromatic group” is not particularly limited as long as it falls within the range defined above. Specifically, aniline, aminobenzoic acid, cyanoaniline,
Aminophenol, aspartic acid, aminocresol, aminocinnamic acid, 4-fluoroanthranic acid, fluorophenylglycine, 2,2-bis-4-aminophenyl-3'-hydroxyphenylpropane, aminosalicylic acid, alanine, aminocaproic acid , Cysteamine, allylamine, monoethanolamine, phenylalanine, aminoanthraquinone, cyclohexylamine, 2,5-dimethoxyaniline, laurylamine, naphthylamine, oxyphenylalanine, 1- (3-aminopropyl) -1,1,3,3-pentane An example is methyldisiloxane.

Examples of the "aromatic solvent having a solubility parameter of 8.5 to 9.5" include toluene, xylene, ethylbenzene, chlorobenzene and the like, and may be in one kind or in a mixture of plural kinds. .

Examples of the "polar solvent having a solubility parameter of 9.0 to 12.1" include dimethylacetamide, diethylacetamide, dimethylformamide, diethylformamide, isophorone, N-methylpyrrolidone and the like. It may be a mixed state of species.

As the “mixed solvent of an aromatic solvent having a solubility parameter of 8.5 to 9.5 and a polar solvent having a solubility parameter of 9.0 to 12.1”, the ratio of the aromatic solvent to the polar solvent is as follows: Those having a mass ratio of 30-70%: 70-30% are preferred.

The method for producing an imide compound according to the present invention comprises:
Reacting a carboxylic anhydride of formula (1), formula (4) or formula (6) with an amino compound represented by formula (2),
In a method for producing an imide compound of the formula (3), (5) or (7), 9,10-dihydro-oxa-10
An aromatic solvent having a solubility parameter of 8.5 to 9.5 (preferably 8.5 to 9.0) and a solubility parameter of 9.0 to 12.1 (in the presence of -phosphaphenanthrene-10-oxide); Preferably, a step of performing a reaction (dehydration condensation reaction) at 130 to 160 ° C (preferably 140 to 160 ° C) in a mixed solvent with a polar solvent of 10.0 to 12.1) is included. Then, after confirming that water necessary for producing the corresponding imide compound is distilled out by the dehydration reaction, in a linear or branched alcohol having 1 to 4 carbon atoms, in a poor solvent such as hydrous alcohol or The corresponding imide compound can be obtained by precipitating the imide compound in water, filtering, washing and filtering again with a poor solvent if necessary, and drying at 80 to 150 ° C.

Here, 9,10-dihydro-oxa-1
The amount of 0-phosphaphenanthrene-10-oxide is preferably from 0.2 to 10 parts based on the mass of the reactants.

The carboxylic anhydride or amino compound used as a raw material is not limited to one kind, but may be a mixture of two or more.

The method for producing an imide compound of the present invention is preferably carried out under an inert gas stream. As the inert gas, nitrogen gas and argon gas are preferable.

A novel (meth) acrylated imide compound can be obtained by introducing a (meth) acrylate group into the imide compound obtained according to the production method of the present invention. In particular, the imide compounds of the formulas (8), (9) and (10) are particularly excellent in heat resistance and solubility, and are extremely useful as a photoresist material for electronic materials and an interlayer insulating film.

The (meth) acrylated imide compounds of the formulas (8), (9) and (10) can be converted into imide compounds of the formulas (3), (5) and (7) by conventional means, respectively. Can be obtained from For example, a method of reacting a (meth) acrylic halide with one of the substituents on R ₂ (for example, a hydroxyl group) can be mentioned.

[0047]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 A reaction flask equipped with a cooling condenser, a thermometer, a stirrer, a dropping funnel, and a gas injection tube equipped with a test tube was charged with 31.0 g of oxydiphthalic anhydride and xylene 12
Then, 0 g and 80 g of dimethylacetamide were added, and nitrogen gas was introduced through a gas blowing tube and stirred. Then, 21.8 g of p-aminophenol was added at 10-30 ° C. To this was added 1.2 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 1
The reaction was performed at 30 to 150 ° C. for 3 hours. Then, 3.63 g (calculated value: 3.6 g) of the generated water was removed from the test tube.
After evaporating 120 g of the solvent, 100 g of methanol was added, the mixture was cooled to 10 ° C, and the crystals were filtered and dried at 130 ° C to obtain an imide compound of the following formula (11).

[0049]

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Yield 47.3 g (96% yield) OHV 229.5 (calculated 228.0)

Example 2 In the same apparatus as in Example 1, p-aminobenzoic acid 27.4 was used.
g, 120 g of xylene, 1.2 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, nitrogen gas was introduced, and 31 g of oxydiphthalic anhydride was added to 80 g of dimethylacetamide. Was added at 30 to 45 ° C, and reacted at 140 to 145 ° C for 3.5 hours, and 3.55 g (calculated value 3.6 g) of generated water was removed from the test tube. After removing 120 g of the solvent, 100 ml of hydrated methanol (50/50% by volume) was added.
Was added, and the mixture was cooled to 10 ° C, separated by filtration, and dried at 80 to 140 ° C to obtain an imide compound of the following formula (12).

[0052]

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Yield: 52.9 g (96.5% yield) Decomposition temperature: 416 ° C. Acid value: 205.1 (calculated value: 204.7)

Example 3 Styrene-maleic anhydride 1:
20.2 g of 1 copolymer, 100 g of xylene and 50 g of dimethylformamide were added, and argon gas was introduced through a gas blowing tube and stirred. After adding 5.7 g of allylamine to this at 10 to 30 ° C, 0.5 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added. The reaction was performed for 5 hours. Then, 1.78 g of the generated water (calculated value 1.8)
g) was removed from the test tube. Thereafter, 100 g of the solvent was distilled off, and the residue was washed with 100 ml of water.
After washing with 0 ml, the crystals were separated by filtration and dried at 130 ° C. to obtain an imide compound of the following formula (13).

[0055]

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Yield: 23.2 g (96.3% yield) Decomposition temperature: 393 ° C.

Example 4 In the same apparatus as in Example 1, oxydiphthalic anhydride 31 was added.
g, xylene 120 g, dimethylformamide 80 g
Nitrogen gas is introduced into the container containing glycine 1 at 25 ° C.
To 5.1 g of the mixture, 1 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was added, and the mixture was reacted at 130 to 143 ° C. for 3.5 hours. 6 g (calculated value 3.6 g) was removed from the test tube. After the solvent was distilled off, the residue was washed with a mixture of 50 g of methanol and 50 g of water, cooled to 10 ° C., and dried at 135 ° C. to obtain an imide compound of the following formula (14).

[0058]

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Yield 40.7 g (Yield 95.8%) Acid value 264.1 (Calculated value 264.0) Decomposition temperature 385 ° C

Example 5 The same apparatus as in Example 1 was charged with 46.4 g of tetrabromophthalic anhydride, 180 g of xylene, and 120 g of dimethylacetamide.
9,10 g to 10.9 g of aminophenol
1.6 g of dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 130-143
The reaction was carried out at a temperature of 3 ° C. for 3 hours. The generated water (1.81 g, calculated value: 1.8 g) was removed from the test tube. The reaction product was cooled to 10 ° C., the crystals separated by filtration were washed with 200 g of methanol, filtered and dried at 140 ° C. to obtain an imide compound of the following formula (15).

[0061]

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Yield 54.7 g (calculated 55.5 g) Yield 98.6% OHV 100.9 (calculated 101.08) Decomposition temperature 362 ° C.

Example 6 30 g of N, N-bis (hydroxyphenyl) oxydiphthalimide obtained in Example 1 was cooled,
The mixture was placed in a reaction tube equipped with a thermometer, a stirrer, a dropping funnel, and a gas blowing tube. Furthermore, dimethylacetamide 20
Then, 0 g and 12 g of tetraethylamine were charged, and nitrogen gas was passed through a gas blowing tube and stirred. After cooling to 0 ° C., a mixture of 12.8 g of methacrylic acid chloride and 0.2 g of hydroquinone was dropped from a dropping funnel. After dropping, the mixture was aged at 10 ° C. or lower for 3 hours, poured into 400 g of ice water, and crystallized. After filtration, the precipitate was dried at 50 ° C. or lower to obtain a methacrylated imide compound represented by the following formula (16).

[0064]

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Yield 35.6 g (calculated value 39.5 g) Yield 90.0% Bromine value 44.5 (calculated value 45.9) Decomposition temperature 330 ° C.

Continued on the front page F-term (reference) 4C069 AC31 BB03 BC12 4C204 AB04 BB03 CB04 DB30 EB03 FB17 FB23 GB25 GB40 4J100 AA02Q AA06Q AA08P AA09P AA15Q AB02Q AK31P AK32P AK33P BA03H BA16H BA40H43 JA03H

Claims (6)

[Claims] (1) Formula (1): (Wherein R ₁ represents an aliphatic group, an alicyclic group or an aromatic group), and a carboxylic acid monoanhydride represented by the formula (2): (Wherein, R ₂ represents an aliphatic group, an alicyclic group or an aromatic group; A represents a carboxyl group, a hydroxyl group, a mercapto group, a cyano group, a C ₁ -C ₄ linear or branched alkyl group) A carboxylic acid ester group having a methoxy group, -Si
(CH ₃ ) ₂ —O—Si (CH ₃ ) ₃ or a halogen atom; n represents an integer of 0 to 4) to react with an amino compound represented by the formula (3): ] (Wherein R ₁ , R ₂ , A, and n are as described above), wherein 9,10-dihydro-oxa-0-phosphaphenanthrene-10- In the presence of an oxide, a mixed solvent of an aromatic solvent having a solubility parameter of 8.5 to 9.5 and a polar solvent having a solubility parameter of 9.0 to 12.1
A method characterized by reacting at 160 ° C. 2. Formula (4): (Wherein R ₁ is as defined in claim 1) and a carboxylic dianhydride represented by the formula (2): (Wherein, R ₂ , A, and n are as defined in claim 1)
By reacting with an amino compound represented by the formula (5): (Wherein R ₁ , R ₂ , A, and n are as defined in claim 1), wherein 9,10-dihydro-oxa-0-phosphaphenanthrene is provided. In the presence of -10-oxide, in a mixed solvent of an aromatic solvent having a solubility parameter of 8.5 to 9.5 and a polar solvent having a solubility parameter of 9.0 to 12.1, 130 to
A method characterized by reacting at 160 ° C. 3. Formula (6): Wherein R ₁ is as defined in claim 1; m is 1
A carboxylic anhydride copolymer represented by:
Formula (2): (Wherein, R ₂ , A, and n are as defined in claim 1)
By reacting with an amino compound represented by the formula (7): (Wherein R ₁ , R ₂ , A, and n are as defined in claim 1; and m is as defined above), wherein 9,10-dihydro- In a mixed solvent of an aromatic solvent having a solubility parameter of 8.5 to 9.5 and a polar solvent having a solubility parameter of 9.0 to 12.1, in the presence of oxa-10-phosphaphenanthrene-10-oxide, 130 ~
A method characterized by reacting at 160 ° C. 4. Formula (8): Wherein R ₁ , R ₂ and A are as described above;
R ₃ represents hydrogen or a methyl group)
An imide compound represented by the formula: 5. Formula (9): (Wherein, R ₁ , R ₂ , and A are as defined in claim 1;
p and R ₃ are as defined in claim 4). 6. Formula (10): (Wherein, R ₁ , R ₂ , and A are as defined in claim 1;
m is as defined in claim 3; p and R ₃ are as defined in claim 4).