JP2003012615A - New diaminodihydroxybenzene and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new diaminodihydroxybenzene, and to provide a method for producing the diaminodihydroxybenzene. SOLUTION: [1] This diaminodihydroxybenzene is represented by the general formula (1). [wherein, R<1> is H or a hydrocarbon; R<2> is a hydrocarbon, OR<3> or NR<4> R<5> (R<3> to R<5> are each the same or different and H or a hydrocarbon)]. [2] The method for producing the diaminodihydroxybenzene represented by the general formula (1) is characterized by reducing a dinitrodihydroxybenzene represented by the general formula (2). [wherein, R<1> and R<2> are the same as those defined in the general formula (1)].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin material, a resin additive, a novel diaminodihydroxybenzene and dinitrodihydroxybenzene useful as a photosensitive resin, and a method for producing the same.

[0002]

2. Description of the Related Art There have been no reports of diaminodihydroxybenzenes represented by the general formula (1) and dinitrodihydroxybenzenes represented by the general formula (2).

Further, diaminodihydroxybenzenes represented by the general formula (1) as resin raw materials, additives, or photosensitive resin materials, especially for urethane and polyimide, are expected to have characteristic physical properties, but synthetic examples are reported. Was not done.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide novel diaminodihydroxybenzenes which, when used as a resin raw material or a resin additive, show characteristic physical properties as compared with conventional amines. . Furthermore, it is to provide a method capable of industrially producing the novel compound.

[0005]

Means for Solving the Problems The present inventors have searched various novel diaminodihydroxybenzenes and have a carbonyl group, an amide group or an acyl group by dinitration and reduction using a dihydroxybenzoic acid derivative as a raw material. New diaminodihydroxybenzenes were synthesized. In addition, the diaminodihydroxybenzenes have a characteristic that oxidative decomposition is suppressed as compared with diaminoresorcin. That is, the present invention is [1] diaminodihydroxybenzenes represented by the general formula (1).

[0006]

[Chemical 3]

(In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group. R ² represents a hydrocarbon group, OR ³ or NR ⁴ R ⁵ (R ³ ~
R ⁵ are the same or different and each represents a hydrogen atom or a hydrocarbon group) [2] Dinitrodihydroxybenzenes represented by the general formula (2).

[0008]

[Chemical 4]

(Wherein R ¹ and R ² are as defined for the general formula (1)) [3] The general formula (1) characterized by reducing the dinitrodihydroxybenzenes represented by the general formula (2). The manufacturing method of the diamino dihydroxy benzenes shown by these. [4] The diaminodihydroxybenzenes according to [1], wherein R ¹ is a hydrogen atom and R ² is a hydroxyl group,
[2] The dinitrodihydroxybenzenes described.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. In formulas (1) and (2), R ¹ represents a hydrogen atom or a hydrocarbon group. R ² is a hydrocarbon group, OR ³ or NR ⁴
R ⁵ (R ^{3 to} R ⁵ are the same or different and represent a hydrogen atom or a hydrocarbon group). Examples of the hydrocarbon group represented by R ^{1 to} R ⁵ above include a lower alkyl group, a lower alkenyl group,
Represents an aralkyl group and an aryl group. The lower alkyl group may be a linear, branched or cyclic C1-C8 substituent such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert. -
A butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like.

The lower alkenyl group is a linear or branched alkenyl group having 2 to 6 carbon atoms, and examples thereof include vinyl group, allyl group, isopropenyl group, 4-pentenyl group,
5-hexenyl group and the like can be mentioned. Examples of the aralkyl group include a benzyl group, a phenethyl group, a benzhydryl group, a phenylpropyl group and the like. Moreover, examples of the aryl group include a phenyl group and a naphthyl group.

As a concrete example of the general formula (1), 3,
5-diamino-2,6-dihydroxybenzoic acid, 3,5
-Methyl diamino-2,6-dihydroxybenzoate,
Ethyl 3,5-diamino-2,6-dihydroxybenzoate, 3,5-diamino-2,6-dihydroxy-4-methylbenzoic acid, 3,5-diamino-2,6-dihydroxy-4-isopropylbenzoic acid , 3,5-diamino-
2,4-dihydroxybenzoic acid, 3,5-diamino-
Methyl 2,4-dihydroxybenzoate, 3,5-diamino-2,4-dihydroxy-6-methylbenzoic acid, 3,
5-diamino-2,4-dihydroxy-6-ethylbenzoic acid, 2,4-diamino-3,5-dihydroxybenzoic acid, methyl 2,4-diamino-3,5-dihydroxybenzoate, 2,4-diamino Ethyl-3,5-dihydroxybenzoate, 2,4-diamino-3,5-dihydroxy-6-methylbenzoic acid, 2,4-diamino-3,5-dihydroxy-6-isopropylbenzoic acid, 3,5- Diamino-2,6-dihydroxybenzamide, N, N-dimethyl-3,5-diamino-2,6-dihydroxybenzamide, N, N-diethyl-3,5-diamino-2,6-dihydroxybenzamide,

3,5-Diamino-2,6-dihydroxy-4-methylbenzamide, 3,5-diamino-2,6
-Dihydroxy-4-isopropylbenzamide,
3 ', 5'-diamino-2', 6'-dihydroxyacetophenone, 3 ', 5'-diamino-2', 6'-dihydroxypropiophenone, 3 ', 5'-diamino-2', 6'- Dihydroxybenzophenone, 3 ', 5'-diamino-
2 ', 4'-dihydroxyacetophenone, 3', 5'-diamino-2 ', 4'-dihydroxypropiophenone,
Mention may be made of 3 ', 5'-diamino-2', 4'-dihydroxybenzophenone.

As a concrete example of the general formula (2), 3,
5-dinitro-2,6-dihydroxybenzoic acid, 3,5
-Methyl dinitro-2,6-dihydroxybenzoate,
Ethyl 3,5-dinitro-2,6-dihydroxybenzoate, 3,5-dinitro-2,6-dihydroxy-4-methylbenzoic acid, 3,5-dinitro-2,6-dihydroxy-4-isopropylbenzoic acid , 3,5-dinitro-
2,4-dihydroxybenzoic acid, 3,5-dinitro-
Methyl 2,4-dihydroxybenzoate, 3,5-dinitro-2,4-dihydroxy-6-methylbenzoic acid, 3,
5-Dinitro-2,4-dihydroxy-6-ethylbenzoic acid, 2,4-dinitro-3,5-dihydroxybenzoic acid, methyl 2,4-dinitro-3,5-dihydroxybenzoate, 2,4-dinitro Ethyl-3,5-dihydroxybenzoate, 2,4-dinitro-3,5-dihydroxy-6-methylbenzoic acid, 2,4-dinitro-3,5-dihydroxy-6-isopropylbenzoic acid, 3,5- Dinitro-2,6-dihydroxybenzamide, N, N-dimethyl-3,5-dinitro-2,6-dihydroxybenzamide, N, N-diethyl-3,5-dinitro-2,6-dihydroxybenzamide,

3,5-Dinitro-2,6-dihydroxy-4-methylbenzamide, 3,5-dinitro-2,6
-Dihydroxy-4-isopropylbenzamide,
3 ', 5'-dinitro-2', 6'-dihydroxyacetophenone, 3 ', 5'-dinitro-2', 6'-dihydroxypropiophenone, 3 ', 5'-dinitro-2', 6 '
-Dihydroxybenzophenone, 3 ', 5'-dinitro
-2 ', 4'-dihydroxyacetophenone, 3', 5'-
Dinitro-2 ', 4'-dihydroxypropiophenone and 3', 5'-dinitro-2 ', 4'-dihydroxybenzophenone can be mentioned.

The diaminodihydroxybenzenes represented by the general formula (1) can be easily derived by reducing the corresponding dinitrodihydroxybenzenes. The reduction method may be any method as long as it reduces a nitro group to an amino group, for example, palladium-carbon, Raney nickel catalyst, platinum catalyst, ruthenium catalyst,
Catalytic hydrogenation reaction in the presence of heavy metal catalysts such as rhodium alumina, reduction method in the presence of metals such as zinc, iron and tin chloride under acidic conditions, sodium sulfide, sodium hydrosulfide, sodium dithionite, ammonium sulfide, etc. The method using the sulfide of is mentioned. The catalytic hydrogenation reaction is preferred because of the ease of post-treatment. The reaction conditions are not particularly limited and can be carried out according to conventional methods. Taking the catalytic hydrogenation reaction as an example, in the presence of the above-mentioned heavy metal catalyst,
The reaction is performed in a hydrogen gas atmosphere.

The amount of the catalyst used is not particularly limited, but is usually 0.01 mol% to 10 equivalents, preferably 0.
1 mol% to 1 equivalent, more preferably 1 mol% to 50
It is mol%.

The pressure of hydrogen during the reaction is 0.1 MPa to 2 MPa.
The pressure is 0 MPa, preferably 0.1 MPa to 10 MPa, more preferably 0.1 MPa to 5 MPa. The reaction temperature is -50 to 100 ° C, preferably -30 to 70 ° C, more preferably 0 to 50 ° C. Reaction time is 0.01-1
It is 0 hours, preferably 0.05 to 5 hours, more preferably 0.1 to 3 hours.

After the reaction, the target solution can be obtained as crude crystals by adding the reaction solution to water and filtering out the precipitated crystals, or by extracting with an organic solvent and distilling off the solvent. If necessary, the catalyst may be removed by filtering the solution before depositing the target substance. When further purification is required, the purity can be increased by recrystallization or the like. The solvent used for recrystallization is not particularly limited, but water, hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as toluene, xylene or ethylbenzene,
Examples thereof include alcohols such as methanol, ethanol, propanol or butanol, and esters such as acetic acid ester. These solvents may be used alone or as a mixture.

The dinitrodihydroxybenzenes represented by the general formula (2) can be obtained by dinitration of the corresponding dihydroxybenzenes. Examples of the raw material dihydroxybenzenes include 2,6-dihydroxybenzoic acid,
Methyl 2,6-dihydroxybenzoates, ethyl 2,6-dihydroxybenzoates, 2,6-dihydroxy-4
-Methylbenzoic acid, 2,6-dihydroxy-4-isopropylbenzoic acid, 2,4-dihydroxybenzoic acid, 2,
Methyl 4-dihydroxybenzoate, ethyl 2,4-dihydroxybenzoate, propyl 2,4-dihydroxybenzoate, 2,4-dihydroxy-6-methylbenzoic acid,
2,4-dihydroxy-6-ethylbenzoic acid, 3,5-
Dihydroxybenzoic acid, methyl 3,5-dihydroxybenzoates, ethyl 3,5-dihydroxybenzoate,

3,5-Dihydroxy-4-methylbenzoic acid, 3,5-dihydroxy-4-isopropylbenzoic acid, 2,6-dihydroxybenzamide, N, N-dimethyl-2,6-dihydroxybenzamide, N, N -Diethyl-
2,6-dihydroxybenzamide, 2,6-dihydroxy-4-methylbenzamide, 2,6-dihydroxy-4-isopropylbenzamide, 2 ', 6'-dihydroxyacetophenone, 2', 6'-dihydroxypropiophenone, 2 ', 6'-dihydroxybenzophenone,
2 ', 4'-dihydroxyacetophenone, 2', 4'-dihydroxypropiophenone, 2 ', 4'-dihydroxybenzophenone and the like can be mentioned.

Any nitration method may be used as long as it is an ordinary method for nitrating a benzene ring. For example, nitric acid-sulfuric acid, nitric acid or the like, a method using a nitrate and an acid, or nitric acid-acetic anhydride is used. Examples thereof include a method of using, a method of using a nitrogen oxide such as N ₂ O ₄ , and a method of nitrosating and then oxidizing. The method using nitric acid is preferable from the economical point of view.

The reaction conditions are not particularly limited, and the reaction can be carried out according to the conventional method, but it is usually carried out in an atmosphere of an inert gas such as nitrogen or argon, and the amount of the nitrating agent used is 2 with respect to the raw material. It is enough if more than equivalent, but 2
-20 equivalents, preferably 2.2-10 equivalents. The reaction temperature is -50 to 100 ° C, preferably -30 to 70 ° C.
More preferably, it is 0 to 50 ° C. Reaction time is 0.0
It is 1 to 10 hours, preferably 0.05 to 5 hours, and more preferably 0.1 to 3 hours.

After the reaction, the target solution can be obtained as a crude crystal by adding the reaction solution to water and separating the precipitated crystal by filtration, or by extracting with an organic solvent and distilling off the solvent. When further purification is required, the purity can be increased by recrystallization or the like. The solvent used for recrystallization is not particularly limited, but includes water, hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as toluene, xylene or ethylbenzene, methanol, ethanol,
Examples thereof include alcohols such as propanol and butanol, and esters such as acetic acid ester. These solvents may be used alone or as a mixture.

The novel diaminodihydroxybenzenes of the present invention are suitable for use in the production of photosensitive resin compositions, especially positive-working photosensitive resin compositions. The composition is generally one containing polyamides containing diaminodihydroxybenzenes provided in the present invention and a photosensitive diazoquinone compound, but bisphenols may be added as a dissolution accelerator. Any polyamide containing the diaminodihydroxybenzenes may be used as the polyamide containing the diaminodihydroxybenzenes provided in the present invention. For example, the polyamide represented by the general formula (3)

[0026]

[Chemical 5]

(Wherein R ¹ and R ² are as defined in the general formula (1). Y is a divalent aliphatic or cyclic compound group, E is an aliphatic group having at least one alkenyl group or alkynyl group, or Cyclic compound group, m represents 2 to 500) or general formula (4)

[0028]

[Chemical 6]

(Wherein R ¹ , R ² , Y, E and m are as defined in the general formula (3), Z is the following structure,

[0030]

[Chemical 7]

(Wherein R ⁶ and R ⁷ are divalent organic groups, R ⁸ and R ⁹ are monovalent organic groups), and a and b are mole fractions, and a + b = 100 moles. %). Polyamides containing a siloxane structure represented by

The polyamides represented by the general formulas (3) and (4) are obtained by adding the diaminodihydroxybenzene (in the case of the general formula (4), a diamine having a Z structure) and a dicarboxylic acid having a Y structure, It is composed of an acid anhydride having a structure of E, and when this polyamide is heated at about 300 to 400 ° C., it undergoes a dehydration ring closure and changes into a heat resistant resin called polybenzoxazole. Y in the general formulas (3) and (4) is, for example, an ethylene group, a hexylene group, a cyclohexylene group,
p-phenylene group, m-phenylene group, o-phenylene group,

[0033]

[Chemical 8]

(In the formula, A is --CH _2- , --C (CH ₃ ) _2- , --O
-, - S -, - SO 2 -, - CO -, - NHCO -, - C (CF 3) 2 -
Represents), but is not limited thereto.
Further, E in the general formulas (3) and (4) is, for example,

[0035]

[Chemical 9]

(In the formula, R ¹⁰ is H, --CH ₂ CH ₃ , --CH ₂
CH═CHCH ₃ , —CH ₂ C≡CCH ₃ , R ¹¹ represents H, —CH ₃ ) and the like, but are not limited thereto.
The polyamide is synthesized by reacting a diaminodihydroxybenzene (in the case of the general formula (4), a diamine having a Z structure) with a dicarboxylic acid derivative having a Y structure to synthesize a polyamide, ), At least 1 alkenyl group or alkynyl group represented by E of (4)
The terminal amino group is capped with an acid anhydride having one unit.

Further, Z in the general formula (4) is, for example,

[0038]

[Chemical 10]

However, the present invention is not limited to these. Z in the general formula (4) is used when particularly excellent adhesion is required for a substrate such as a silicon wafer. The photosensitive diazoquinone compound used in the present invention is
It is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is disclosed in US Pat. Nos. 2,772,972 and 2,797,213.
No. 3,669,658.

The positive photosensitive resin composition may contain bisphenol compounds in order to increase the dissolution rate in the exposed area and improve the sensitivity. Examples of these are bis (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, (4-hydroxyphenyl) (3-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethyl) Phenyl) propane, 3,3-bis (4-hydroxy-3-methylphenyl) pentane,
Bis (2-hydroxy-3,5-dimethylphenyl) methane, 2,2-bis (2-hydroxy-3,5-dimethylphenyl) -3-methylbutane, 1,1-bis (2-
Hydroxy-3,5-dimethylphenyl) ethane, 1,
Examples thereof include 1-bis (2-hydroxy-3-methyl-5-tert-butylphenyl) ethane, but are not limited thereto.

The photosensitive resin composition in the above description includes
If necessary, additives such as a leveling agent and a silane coupling agent can be added. In the present invention, these components are dissolved in a solvent to form a varnish for use. The photosensitive resin composition according to the above description is useful not only for semiconductor applications but also for interlayer insulation of multilayer circuits, cover coats of flexible copper clad boards, solder resist films, liquid crystal alignment films, and the like.

Examples will be shown below, but the present invention is not limited to these examples.

[0043]

Example 1 Synthesis of 3,5-dinitro-2,6-dihydroxybenzoic acid In a 50 ml three-necked flask, 6.16 g (40 mmol) of 2,6-dihydroxybenzoic acid and 50 ml of acetic acid were added, and a nitrogen atmosphere was added. While stirring at room temperature, add 30% of 60% nitric acid
It dripped over minutes. The temperature of the reaction solution was raised to 37 ° C. After stirring at room temperature for 2 hours, ethyl acetate was added to the reaction solution to extract the desired product. After washing the organic phase three times with saturated saline,
The solvent was concentrated. Hexane was added at 0 to 5 ° C to precipitate crystals. The crystals were filtered off and dried under reduced pressure at room temperature to give 8.46 g (34 mmol, yield 85%, LC) of pale yellow crystals of 3,5-dinitro-2,6-dihydroxybenzoic acid.
Purity 98%) was obtained. The structure and physical properties of the target product are as follows.

[0044]

[Chemical 11]

Melting point 300 ° C. or higher ¹ H-NMR (CD ₃ OD) δ: 8.90 (s 1H) FD-mass 244 (M ⁺ )

(Example 2) 3,5-diamino-2,6-
Synthesis of dihydroxybenzoic acid 3,5-dinitro-2,6-in a 50 ml three-necked flask.
Dihydroxybenzoic acid 2.44 g (10 mmol), 5% palladium-carbon 0.4 g, ethanol 20 ml, acetic acid 5 m
1 was added, and the mixture was stirred at 75 ° C. under normal pressure and hydrogen atmosphere. Some crystals precipitated during the reaction. After absorbing a calculated amount of hydrogen (after 1.5 hours), the mixture was cooled to room temperature, and the reaction solution was filtered to remove palladium-carbon. The crystals attached to palladium-carbon were extracted with N, N-dimethylformamide and combined with the filtrate. After concentrating the obtained reaction solution, hexane was added to precipitate crystals. After the crystals were filtered off, the crystals were dried under reduced pressure at room temperature to obtain 1.75-purple crystals of 3,5-diamino-2,6-dihydroxybenzoic acid.
g (9.1 mmol, yield 91%, LC purity 98%) was obtained.
The structure and physical properties of the target product are as follows.

[0047]

[Chemical 12]

Melting point 300 ° C. or higher ¹ H-NMR (CD ₃ SOCD ₃ ) δ: 5.89 (s 1H), 8.85 (s, 2H),
9.55 (s, 2H), 13.63 (s, 1H) FD-mass 184 (M ⁺ )

[0049]

Industrial Applicability According to the present invention, when used as a resin raw material or a resin additive, it is possible to provide a novel diaminodihydroxybenzene which exhibits physical properties more characteristic than conventional amines, and to industrially produce the novel compound. I was able to provide a way to do it at the same time.

Continued front page    F-term (reference) 4H006 AA02 AC52 BA25 BA32 BA61                       BB11 BB14 BC10 BC11 BC19                       BE20                 4H039 CA71 CB30                 4J001 DA01 DB01 DB04 DC10 DC16                       DD02 DD05 DD07 DD08 EB02                       EB30 EB44 EB55 EB56 EB57                       EB58 EB59 EB60 EC44 EC45                       JA17 JA20                 4J002 AA001 EN106

Claims (4)

[Claims] 1. Diaminodihydroxybenzenes represented by the general formula (1). [Chemical 1] (In the formula, R ¹ represents a hydrogen atom or a hydrocarbon group. R ² represents a hydrocarbon group, OR ³ or NR ⁴ R ⁵ (R ^{3 to} R ⁵ are the same or different and represent a hydrogen atom or a hydrocarbon group. Represents) represents) 2. A dinitrodihydroxybenzene represented by the general formula (2). [Chemical 2] (In the formula, R ¹ and R ² are as defined for the general formula (1)) 3. A method for producing diaminodihydroxybenzenes represented by general formula (1), which comprises reducing dinitrodihydroxybenzenes represented by general formula (2). 4. The diaminodihydroxybenzenes according to claim 1 and the dinitrodihydroxybenzenes according to claim ² , wherein R ¹ is a hydrogen atom and R ² is a hydroxyl group.