JP2001163870A - Method for producing 9,9-disubstituted-xanthene-2,3,6,7- tetracarboxylic acid and dianhydride thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a 9,9-disubstituted-xanthene-2,3,6,7- tetracarboxylic acid in high yield in a short process without the need of any special equipment, and to provide a method for producing the corresponding dianhydride of the above compound. SOLUTION: This method for producing a 9,9-disubstituted-xanthene-2,3,6,7- tetracarboxylic acid comprises the following process: a 3,4-dialkylphenol is reacted with a gem-bis(4-hydroxyphenyl)alkane of the general formula (1), wherein, R1 and R2 are each a univalent organic group or a derivative thereof in the presence of an acid catalyst to form a hexaalkylxanthene derivative of the general formula (2), wherein, R1 and R2 are each a univalent organic group; and R3, R4, R5 and R6 are each an alkyl, followed by oxidation of the side chains respectively shown by R3, R4, R5 and R6 to obtain the objective 9,9- disubstituted-xanthene-2,3,6,7-tetracarboxylic acid of the general formula (3), wherein, R1 and R2 are each a univalent organic group. The other objective method for producing the corresponding dianhydride of the above compound is also provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin having high i-ray transmittance, high-speed developability, high resolution, and high dimensional accuracy used for forming an interlayer insulating film and a surface protective film of a semiconductor device. The present invention relates to a method for producing tetracarboxylic acid and a dianhydride thereof, which are useful as a material for a polyimide and a precursor thereof having a low thermal expansion and a low residual stress, which are used for a composition.

[0002]

2. Description of the Related Art In recent years, in the semiconductor industry, an organic material having excellent heat resistance, such as a polyimide resin, has been used as an interlayer insulating material which has conventionally been formed using an inorganic material, taking advantage of its characteristics. Have been. However, the formation of circuit patterns on semiconductor integrated circuits and printed circuit boards is complicated and diversified, such as the formation of a resist material on the base material surface, removal of unnecessary portions by exposing and etching predetermined portions, and cleaning of the substrate surface. Therefore, development of a heat-resistant photosensitive material that can use a necessary portion of a resist as an insulating material as it is even after pattern formation by exposure and development is desired.

As these materials, for example, heat-resistant photosensitive materials using photosensitive polyimide, cyclized polybutadiene or the like as a base polymer have been proposed. In particular, photosensitive polyimide has excellent heat resistance and eliminates impurities. Has attracted particular attention because of its ease of use. As such a photosensitive polyimide, a system comprising a polyimide precursor and a dichromate (Japanese Patent Publication No. 49-17374) was first proposed, but this material has practical photosensitivity. In addition, it has advantages such as high film-forming ability, but lacks storage stability and has drawbacks such as chromium ions remaining in polyimide, and thus has not been put to practical use.

In order to avoid such a problem, for example, a method of mixing a compound having a photosensitive group with a polyimide precursor (Japanese Patent Laid-Open No. 54-109828) discloses a method in which a functional group and a photosensitive group in the polyimide precursor are mixed. A method of reacting with a functional group of a compound having a compound to give a photosensitive group (JP-A-56-2
No. 4343, Japanese Patent Application Laid-Open No. Sho 60-100143)
And so on.

[0005] However, these photosensitive polyimide precursors use a basic skeleton as an aromatic monomer having excellent heat resistance and mechanical properties. Due to the absorption of the polyimide precursor itself, its transparency in the ultraviolet region is low. Therefore, the photochemical reaction in the exposed portion cannot be performed sufficiently effectively, resulting in low sensitivity and deterioration of the pattern shape. In recent years, as the integration of semiconductors has increased, processing rules have become increasingly smaller, and there has been a tendency for higher resolution to be required.

For this reason, a conventional contact / proximity exposure machine using parallel rays has been replaced by a 1: 1 projection exposure machine called a mirror projection and a reduction projection exposure machine called a stepper. The stepper utilizes a monochromatic light such as an excimer laser and a high-power oscillation line of an ultra-high pressure mercury lamp. Until now, g-line steppers using visible light (wavelength: 435 nm) called g-line of ultra-high pressure mercury lamps have been the mainstream stepper. However, in order to respond to the demand for finer processing rules, the stepper used is Needs to be shortened. Therefore, the exposure equipment used is from a g-line stepper (wavelength: 435 nm) to an i-line stepper (wavelength: 3 nm).
65 nm).

However, a conventional photosensitive polyimide base polymer designed for a contact / proximity exposure machine, a mirror projection projection exposure machine, and a g-line stepper has a low transparency for the above-mentioned reason, and particularly has a low i-line. (Wavelength: 365 nm) because there is almost no transmittance.
A proper pattern cannot be obtained with an i-line stepper. In addition, polyimide films for surface protection are required to be thicker in response to LOC (lead-on-chip), which is a high-density mounting method for semiconductor elements. The problem gets worse. Therefore, there is a strong demand for a photosensitive polyimide having a high i-line transmittance and a polyimide pattern having a good pattern shape by an i-line stepper.

The diameter of a silicon wafer serving as a substrate is
As the thermal expansion coefficient increases between polyimide and a silicon wafer, a problem arises in that the warpage of the silicon wafer on which the polyimide as the surface protection film is formed is larger than before. Therefore, there is a strong demand for a photosensitive polyimide having a lower thermal expansion property than conventional polyimides. In general, low thermal expansion can be achieved by making the molecular structure rigid. However, in the case of the rigid structure, the i-line is hardly transmitted, so that the photosensitive characteristics deteriorate.

As a method for improving the transmittance of i-rays, polyimide having fluorine introduced therein (Japanese Patent Laid-Open No. Hei 8-234433) or polyimide having a molecular chain bent (Japanese Patent Laid-Open No. Hei 8-3) is used.
No. 6264) has been proposed. However, polyimide into which fluorine has been introduced has a low adhesive strength to a silicon wafer, and has low reliability when used in a semiconductor device. Also,
Since polyimide having a bent molecular chain has weak intermolecular interaction, the heat resistance is lowered and the thermal expansion coefficient is increased, so that the reliability in the case of a semiconductor device is low.

The present inventors have used a so-called ladder-type tetracarboxylic dianhydride in which two crosslinked portions are formed between two aromatic rings as one method for solving such a problem. A polyimide precursor was found. In this structure, two aromatic rings can be rigidly and linearly connected without a continuous double bond in order to provide both high i-line transmittance and low thermal expansion.

As one of such ladder-type tetracarboxylic dianhydrides, two cross-linking parts are formed from an ether bond and a 2,2-propylidene bond.
-Dimethyl-xanthene-2,3,6,7-tetracarboxylic dianhydride. This compound is known (S. Trofimenko and BC).
Auman, Macromolecules, 2
7, 1136 (1994). ). However, in the synthesis method described in the above-mentioned literature, special equipment is required because hydrofluoric acid is used in the synthesis process, and the total yield is low and it cannot be said that it is a practical synthesis method.

[0012]

The present invention does not require special equipment, can be synthesized in a short process, and has a high yield of 9,9-disubstituted-xanthene-2,3,6,9. 7
To provide a method for producing tetracarboxylic acid and its dianhydride.

[0013]

SUMMARY OF THE INVENTION The present invention relates to a process for preparing a 3,4-dialkylphenol of the general formula (1) in the presence of an acid catalyst.

Embedded image (Wherein, R ¹ and R ² each independently represent a monovalent organic group), and reacted with gem-bis (4-hydroxyphenyl) alkane or a derivative thereof represented by general formula (2):

Embedded image (Wherein, R ¹ and R ² each independently represent a monovalent organic group, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group). Synthesis, and then oxidizing the side chains represented by R ³ , R ⁴ , R ⁵ and R ⁶ , characterized by the general formula (3)

Embedded image (Wherein, R ¹ and R ² each independently represent a monovalent organic group).
The present invention relates to a method for producing 6,7-tetracarboxylic acid.

The present invention also relates to a compound of the general formula (4) wherein the tetracarboxylic acid represented by the general formula (3) further undergoes a dehydration ring closure reaction.

Embedded image (Wherein, R ¹ and R ² each independently represent a monovalent organic group).
The present invention relates to a method for producing 6,7-tetracarboxylic anhydride.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the production method of the present invention,
A 4-dialkylphenol is reacted with gem-bis (4-hydroxyphenyl) alkane represented by the general formula (1) or a derivative thereof. As the 3,4-dialkylphenol, 3,4-dimethylphenol, 3,4-
Diethylphenol, 3,4-dipropylphenol,
Preferred are those having 1 to 6 carbon atoms in the alkyl group, such as 3,4-dibutylphenol,
Among them, 3,4-dimethylphenol is preferred in terms of synthesis and availability.

On the other hand, gem represented by the general formula (1)
In the -bis (4-hydroxyphenyl) alkane or a derivative thereof, the monovalent organic group represented by R ¹ and R ² is a monovalent organic group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group. Alkyl groups, aryl groups such as phenyl groups, fluorinated alkyl groups such as trifluoromethyl groups, methoxymethyl groups, alkoxy-substituted alkyl groups such as dimethoxymethyl groups, etc., among which organic groups having 1 to 6 carbon atoms are preferred. Preferably, an alkyl group having 1 to 4 carbon atoms is more preferable. Specific examples include bisphenol A,
2,2-bis (4-hydroxyphenyl) butane, 3,
3-bis (4-hydroxyphenyl) hexane, 1,1
-Bis (4-hydroxyphenyl) -1-phenylethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1,1-trifluoro-2,2-bis (4-hydroxyphenyl) propane and the like Preferred are bisphenol A, 2,2-bis (4-hydroxyphenyl) butane, 3,3-bis (4-hydroxyphenyl) hexane, 3,3-bis (4-hydroxyphenyl) pentane, and the like.

These compounds are reacted in the presence of an acid catalyst. Examples of acid catalysts include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid,
Organic sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid are preferred.

From the viewpoint of improving the reaction efficiency and the like, 3,4-dialkylphenol is used in an amount of 20 to 6 based on 1 mol of the compound represented by the general formula (1).
It is preferable to use 0 mol, and it is more preferable to use 40 to 50 mol. For the same reason, it is preferable to use 0.3 to 0.6 mol of the acid catalyst per 1 mol of the compound represented by the general formula (1).

[0019] The reaction temperature is preferably from 80 to 150 ° C, more preferably from 100 to 120 ° C. The reaction time is preferably 30 to 50 hours, more preferably 40 to 50 hours. The reaction can be generally performed without a solvent.

By the above reaction, a hexaalkylxanthene derivative represented by the general formula (2) is formed. This product can be purified by various methods. For example, the reaction mixture is diluted with an aromatic hydrocarbon solvent such as toluene, benzene, or xylene, and about 10% by weight of sodium hydroxide,
It can be obtained by washing with an aqueous solution of potassium hydroxide, sodium hydroxide or the like to remove excess acid catalyst and excess 3,4-dialkylphenol, drying over anhydrous magnesium sulfate or the like, and concentrating.

The above method is described in A. J. Car
uso and J.S. L. Lee, J.M. Or
g. Chem. , 62, 1058 (1997).
Have been found as a result of intensive studies as to whether or not they can be applied to the synthesis of intermediates of the compounds produced in the present invention.

Next, R of the compound of the general formula (2)
By oxidizing the side chain represented by ³ , R ⁴ , R ⁵ and R ⁶ , the 9,9-disubstituted compound represented by the above general formula (3) is obtained.
Xanthene-2,3,6,7-tetracarboxylic acid is obtained. This step is carried out, for example, by the method of literature (CS
Marvel and J.M. H. Lassweil
er, J.A. Am. Chem. Soc. , 8
0, 1197 (1958). ).

As the solvent, water, pyridine, a water-pyridine mixture or the like is used. The amount of the solvent refers to the hexaalkylxanthene derivative represented by the general formula (2).
The amount is preferably 0.6 to 1.6 liter, and particularly preferably 1.2 liter, per mole. In this reaction,
Generally, permanganate is used, and potassium permanganate is particularly preferred. The amount of permanganate is 10 to 10 moles of the hexaalkylxanthene derivative.
15 moles are preferred.

The reaction temperature is preferably from 90 to 110 ° C., and the reaction time is preferably from 1 to 2 hours. By the above method, 9,9-disubstituted-xanthene- represented by the general formula (3)
2,3,6,7-tetracarboxylic acid is produced, which can then be fractionated. For example, first, manganese dioxide as a by-product is filtered off by hot filtration, and then the solvent is distilled off under reduced pressure. Can be filtered.

The thus obtained 9,9-disubstituted-xanthene-2,3,6,7-tetracarboxylic acid represented by the general formula (3) is further subjected to a dehydration ring-closure reaction to obtain the compound represented by the general formula (4) The tetracarboxylic dianhydride represented by The dehydration ring closure reaction can be carried out, for example, by adding acetic anhydride and reacting under reflux with heating, or by heating to 180 to 200 ° C. under reduced pressure. If acetic anhydride is used, the amount is 9,9-disubstituted-xanthene-2,
5 to 15 per mol of 3,6,7-tetracarboxylic acid
ml. The tetracarboxylic dianhydride represented by the general formula (4) can be obtained by filtering off the solid produced by the reflux.

According to the present invention, since no hydrofluoric acid is used, a special apparatus is not required, and the desired product can be obtained with a simpler operation and a higher yield.

[0027]

The present invention will be described below with reference to examples. EXAMPLES The first synthesis step is shown in the following formula.

Embedded image

3,4-dimethylphenol (1) (20
0 g, 1.64 mol), bisphenol A (2)
(10.0 g, 43.9 mmol) and a mixture of methanesulfonic acid (2.0 g, 21 mmol) were heated to 100 ° C. and reacted for 40 hours. The reaction mixture was diluted with toluene and washed with a 10% by weight aqueous sodium hydroxide solution.
30 g of anhydrous magnesium sulfate was added and dried. The desiccant was filtered off, and the filtrate was concentrated.
9,9-Hexamethylxanthene was obtained ((3)
(6.73 g, 25 mmol, 57% yield)).

The following synthesis step is shown by the following equation.

Embedded image

2,3,6,7,9,9-Hexamethylxanthene (3) (53.3 g, 200 mmol) was dissolved in pyridine (1600 ml) -water (800 ml) to form a solution. On the other hand, while stirring vigorously with a mechanical stirrer under heating reflux, potassium permanganate (2
(10 g, 1.33 mol). After the addition was completed, the mixture was heated under reflux for an additional hour and filtered through celite.
This solution is concentrated to 300-400 ml, and water 700m
l and 50 ml of a 50% by weight aqueous solution of sodium hydroxide were added thereto, and the mixture was heated under reflux with potassium permanganate (200 g,
(1.27 mol). After completion of the reaction, excess potassium permanganate was decomposed with isopropyl alcohol, filtered through celite, and concentrated by adding concentrated sulfuric acid to the filtrate.
The resulting solid was separated by filtration, washed with water, and air-dried to obtain tetracarboxylic acid (4). Excess amount (350ml)
The solution was heated under reflux in acetic anhydride, and the resulting solid was filtered off to obtain an acid anhydride (yield 30%). Further, the filtrate was concentrated to obtain a second crystal (yield 15).
%).

The results of NMR analysis of the obtained acid anhydride were as follows, and it was found that 9,9-dimethylxanthene-2,
It was confirmed that 3,6,7-tetracarboxylic dianhydride was generated. 1H NMR (400 MHz, DMSO-d6) δ
= 1.79 (6H, s), 7.84 (2H, s),
8.47 (2H, s).

Comparative Example Trofimenko and B.A. C. A
uman, Macromolecules, 27,
The synthesis process described in 1136 (1994) is as follows.

Embedded image

The yield from this method is only 8% from the precursor of bis (3,4-dimethylphenyl) ether. In contrast, according to the method of the present invention, 2
It can be produced in a high yield of 6%.

[0034]

According to the production method of the present invention, 9,9-disubstituted-xanthene-2,3,6,7-tetracarboxylic acid can be produced in a short process and in a high yield without requiring special equipment. The acid and its dianhydride are obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C062 HH17 4C071 AA01 AA08 CC13 EE05 FF15 GG01 HH08 KK01 KK11 KK14 LL03 LL07 4J043 PA02 PB15 QB31 TA14 ZA31 ZA35 ZA36 ZA46 ZA51 ZB11 ZB47

Claims (2)

[Claims] (1) A 3,4-dialkylphenol and a compound of the formula (1) in the presence of an acid catalyst. (Wherein, R ¹ and R ² each independently represent a monovalent organic group), and reacted with gem-bis (4-hydroxyphenyl) alkane or a derivative thereof to obtain a compound represented by the general formula (2). ] (Wherein, R ¹ and R ² each independently represent a monovalent organic group, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group). Synthesis, and then oxidizing the side chains represented by R ³ , R ⁴ , R ⁵ and R ⁶ , characterized by the general formula (3) (Wherein, R ¹ and R ² each independently represent a monovalent organic group).
A method for producing 6,7-tetracarboxylic acid. 2. The general formula (4) wherein the tetracarboxylic acid represented by the general formula (3) is further subjected to a dehydration and ring closure reaction. (Wherein, R ¹ and R ² each independently represent a monovalent organic group).
A method for producing 6,7-tetracarboxylic anhydride.