JP2005060350A - Method for producing aromatic carboxylic acid and alkali-soluble resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a raw material for alkali-soluble photosensitive resin composition that permits easy pattern formation and has excellent high heat resistance, high reliability, for example, moisture-resistance reliability, further high transparency and low dielectric constant. <P>SOLUTION: In the presence of a palladium catalyst complex and a base, a compound represented by general formula (1) (wherein R<SB>1</SB>is H, -CO-R<SB>2</SB>or -SO<SB>2</SB>-R<SB>2</SB>) and a compound represented by general formula (2) [wherein R<SB>1</SB>is same as in the general formula (1)] are allowed to react with each other to produce a compound of general formula (3) (wherein n is an integer of 1 or more; R<SB>1</SB>is H or -CO-R<SB>2</SB>or -SO<SB>2</SB>-R<SB>2</SB>). In this case, the base has preferably pKa > 11. The alkali-soluble resin composition is prepared by allowing a compound represented by general formula (3) to react with a compound bearing two or more benzocyclobutene structures in one molecule at 100°C to 200°C with heat and its carboxyl group equivalent is ≤ 400 g/mole. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a carboxylic acid useful as a raw material for an alkali-soluble photosensitive fat composition and an alkali-soluble resin composition.

  Generally, a display element such as a thin film transistor type liquid crystal display element includes a protective film for protecting the element and the wiring, an insulating film for insulating the element and the wiring, a planarizing film for planarizing the element surface, An interlayer insulating film or the like that insulates the multilayered wirings is provided. In recent years, a display device having a new mechanism that realizes a high viewing angle and a high contrast, for example, a liquid crystal display device using an MVA (Multi-domain Vertical Alignment) mode is formed on the electrode surface for controlling the alignment of liquid crystal molecules. New element components such as protrusions and spacers that insulate the electrodes with organic EL elements have appeared. On the other hand, for semiconductor devices and printed wiring boards on which they are mounted, a protective film for protecting semiconductor elements and circuits, an insulating film for insulating between semiconductor elements and circuits, or insulation between multilayered wirings An interlayer insulating film is formed. The materials used for these insulating film and protective film components are heat resistant to withstand the heat history during the processing process, and reliable enough to maintain long-term insulating properties in the temperature and humidity ranges used. Sex is required.

  Furthermore, high transparency is required as a display element material. However, as electronic devices have become lighter, thinner, and smaller in recent years, high definition of display elements and miniaturization and high integration of semiconductor devices and printed wiring boards have been developed. Various technical problems arise in the materials used. For example, with the increase in wiring density and signal speed, interference between signals passing through adjacent wirings has become a problem. Therefore, a material having a low dielectric constant as well as high heat resistance and reliability is required for the insulating layer. However, the polyimide resin that has been used as a conventional heat-resistant and highly reliable insulating material has a conjugated heterocyclic group in its resin skeleton, and this actually contributes to high heat resistance. The dielectric constant of the resin was raised, causing signal interference between highly densified wiring, which was not preferable. Further, since this conjugated heterocyclic group absorbs light, there is a problem that it is difficult to adapt to a display element material that requires high transparency.

  In recent years, benzocyclobutene resins have been developed as resins that can be used for these applications. This uses a compound having a 1,2-dihydrobenzocyclobutene structure to form a crosslinked structure by thermal curing at a maximum of 250 ° C. (see, for example, Non-Patent Document 1). Since this resin has a low dielectric constant and high transparency as well as heat resistance and high reliability, it can be said that the resin is very suitable for use as an insulating material as described above.

  On the other hand, in these semiconductor devices, printed wiring boards, and display elements, high density wiring must be created in a small space, and patterns such as through-holes for penetrating the wiring through the insulating resin Must be formed of a resin layer. As a technique for easily forming such a pattern, use of a photosensitive resin composition has become common. This is a resin composition having photoreactivity, and after selectively forming only the part where the resin layer is to be removed after forming the resin layer, or only the part other than the part where the resin layer is to be removed, development is performed. Only the resin layer is dissolved and removed so that pattern processing can be performed. Conventionally, an organic solvent has been mainly used for dissolution of the resin layer by development or the like. However, in order to ensure a good working environment, a photosensitive resin composition that can be dissolved by an aqueous solution of alkali or the like is required. ing.

Among the above benzocyclobutene resins, photosensitive resins (for example, see Patent Document 1) have been developed, and those capable of alkali development are also disclosed (for example, see Patent Document 2). However, the carboxyl group introduced to develop alkali developability may deteriorate characteristics such as dielectric constant and moisture resistance reliability of the resin layer. Therefore, there is a demand for a novel alkali-soluble photosensitive resin composition that is easy to form a pattern, has high heat resistance, high reliability, high transparency, and low dielectric constant, and can exhibit the characteristics. Raw materials are needed.
Kitamura et al., “Thermosetting Resin”, Synthetic Resin Industry Association, 1994, Vol. 15, No. 2, p. 95-108 JP 11-503248 A (all pages) US Pat. No. 6,361,926 (all pages)

  The present invention can be used for an insulating film, a protective film or an interlayer insulating film material for display elements, semiconductors or printed wirings, and can be easily formed with a pattern, and has high reliability such as high heat resistance and moisture resistance reliability. The present invention relates to a method for producing a carboxylic acid and an alkali-soluble resin composition useful as a raw material for an alkali-soluble photosensitive resin composition having excellent properties, high transparency, and low dielectric constant.

The present invention
[1] A fragrance represented by general formula (3), characterized by reacting a compound represented by formula (1) with a compound represented by general formula (2) in the presence of a palladium catalyst complex and a base. A method for producing an aromatic carboxylic acid,

R ₁ is a hydrogen atom, —CO—R ₂ or —SO ₂ —R ₂ .

n is an integer of 1 or more, and R ₁ is a hydrogen atom, —CO—R ₂ or —SO ₂ —R ₂ .

[2] The method for producing an aromatic carboxylic acid according to item [1], wherein the base has a pka of 11 or more,
[3] A resin obtained by heating and reacting a compound represented by the general formula (3) and a compound having two or more benzocyclobutene structures in one molecule at 100 to 200 ° C., and having a carboxyl group equivalent of 400 g / An alkali-soluble resin, characterized in that it is less than or equal to a mole;
It is.

  By using the alkali-soluble photosensitive resin composition using the raw material of the present invention, pattern formation is easy in a photolithography process using an alkaline aqueous solution, high reliability such as high heat resistance and moisture resistance reliability, and further high transparency, An insulating resin layer having excellent characteristics with a low dielectric constant can be obtained. This insulating resin layer can be used for an insulating film for a display element, a semiconductor or a printed wiring, a protective film or an interlayer insulating film material, and is industrially useful.

The carboxylic acid (general formula (3)) obtained in the present invention is obtained by subjecting the compound represented by the general formula (4) and the compound represented by the general formula (5) to a heating reaction. The method for producing the compound represented by the general formula (3) can use a Heck reaction. The Heck reaction is a coupling reaction of an alkene and an organic halogen compound, particularly an aryl halide, caused by a palladium catalyst. Specifically, for example, the compound represented by formula (4) and the compound represented by formula (5) are heated with stirring in an inert atmosphere in the presence of a solvent, a palladium catalyst and an acid scavenger such as trimethylamine. It can be obtained by reacting.
Moreover, in this invention, you may introduce | transduce a substituent into the compound obtained by heat-reacting the compound shown by Formula (4), and the compound shown by Formula (5).
Specific examples of the substituent introduced include compounds represented by formula (6) and formula (7). In these compounds, since the substituent is bonded via a carbonyl group or a sulfone group, the decarboxylation reaction described later can be more efficiently caused.

(R ₂ is a halogen atom.)

  Examples of the palladium catalyst used in the present invention include palladium acetate, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) palladium diacetate, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium. , Tetrakis (methyldiphenylphosphine) palladium, trans-di-μ-acetobis [2- (di-o-tolylphosphino) benzyl] dipalladium, and the like, which may be used alone or in combination.

  Examples of the phosphorus ligand used in the present invention include triphenylphosphine, 1,3-bis (diphenylphosphino) propane, rac-2,2′-bis (diphenylphosphino) -1,1′-binaphthyl, Examples include tri-o-tolylphosphine, and these may be used alone or in combination.

  Examples of bases as hydrogen halide acceptors used in the present invention include dipentylamine (pka = 11.2), pyrrolidine (pka = 11.2), dibutylamine (pka = 11.3), dibenzoyl Methane (pka = 13.8) and the like can be mentioned, and these may be used alone or in combination.

  An alkali-soluble resin can be produced by heating the carboxylic acid obtained in the present invention and a compound having two or more benzocyclobutene structures in one molecule in a solvent-free or solvent at 100 to 200 ° C., The carboxyl group equivalent is 400 g / mol or less. As long as the carboxyl group equivalent is 400 g / mol or less, there is no particular limitation, but inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and aqueous ammonia used during development, tetramethylammonium hydroxide, ethylamine, triethylamine, and triethanol are used. It becomes soluble in an aqueous solution of an organic alkali such as amine, and an aqueous alkaline solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant is added. When the carboxyl group equivalent is larger than 400 g / mol, the above-described solubility in an aqueous alkaline solution is hardly exhibited, and pattern processing cannot be performed. The amount of carboxyl groups in the resin can be measured by titration of the resin solution using a standard alkaline solution.

  Examples of the compound having two or more benzocyclobutene structures in one molecule used in the present invention include compounds represented by the following formula (8), formula (9), and formula (10). It is not limited. Of these, the compound represented by the general formula (8) is preferable from the viewpoint of mechanical properties of the heat-cured resin.

  The alkali-soluble resin that can be produced from the raw material of the present invention comprises a compound represented by the general formula (3) and a compound having two or more benzocyclobutene structures in one molecule at 100 to 200 ° C. without solvent or in a solvent. What is necessary is just to heat. When the temperature is lower than 100 ° C., the high molecular weight reaction does not occur sufficiently and the film-forming property is deteriorated. On the other hand, if the temperature exceeds 200 ° C., the resin is insolubilized due to three-dimensional crosslinking, and cannot be used. Although depending on the reaction temperature, the reaction time is preferably less than 100 hours. Thereby, an appropriate molecular weight resin can be obtained. If it exceeds 100 hours, the resulting resin will have a high molecular weight, and the three-dimensionalization will proceed, resulting in a decrease in alkali solubility. The molecular weight of these alkali-soluble resins can be measured as a polystyrene-converted value by GPC (gel permeation chromatography), but in order to obtain good solubility and film-forming properties, this value is used as the weight average molecular weight. It is desirable that it is 1000 or more and 30000 or less.

  In addition, during the resin production, the carboxyl group equivalent of the resulting resin is controlled by changing the charging ratio of the compound represented by the general formula (3) and the compound having two or more benzocyclobutene structures in one molecule. be able to. Solvents used for the reaction in a solvent include mesitylene, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl lactate and the like. These may be used alone or in combination. When reacted in a solvent, the reaction product is obtained as a resin solution. When producing a photosensitive resin composition, the resin solution may be used as it is, or a solvent as described above may be further added in consideration of processing workability. When the reaction is carried out in the absence of a solvent, the resulting resin may be dissolved in the solvent as described above to produce a photosensitive resin composition. When an alkali-soluble resin is obtained as a resin solution, the concentration of the resin in the solution is as follows: the weight of the resin solution is heated at 150 ° C. for 60 minutes; I can know.

  The obtained resin is soluble in the alkali solution as described above, and 0.01 to 10 parts by weight of the basic substance and 1,2-based on the alkali-soluble resin and 100 parts by weight of the alkali-soluble resin. When an alkali-soluble photosensitive resin composition containing a photosensitive material having a quinonediazide structure or a 1,2-naphthoquinonediazide structure is applied to a substrate to form a resin layer, exposed, developed, rinsed, post-exposed, and heat cured Carboxyl groups present in the resin layer are removed from the system, but by heating for 0.5 hours or more in a heating temperature range of 100 to 250 ° C., 50% or more of the carboxyl groups in the alkali-soluble resin are decarboxylated. Removed outside the system. The carboxyl group in the resin before and after heat curing can be quantified by comparing the intensity of absorption of the hydroxyl group derived from the carboxyl group in the infrared absorption spectrum of each resin, but the carboxyl group removed by heating However, if it is less than 50%, the dielectric constant and moisture resistance reliability of the resin layer are adversely affected.

  By adding a basic substance to the photosensitive resin composition obtained from the present invention, a decarboxylation reaction of a carboxyl group in an alkali-soluble resin or a carboxyl group generated from a photosensitive material in a resin layer by post-exposure described later Can be promoted. Examples of basic substances include inorganic bases such as sodium hydroxide, potassium hydroxide and soda lime, imidazole derivatives such as 2-methylimidazole, 1-hydroxyethyl-2-alkylimidazoline, 1,5-diazabicyclo [4,3, 0] non-5-ene, 1,8-diazabicyclo [5,4,0] -7-undecene, triethanolamine, triphenylphosphine, and other organic bases can be mentioned, but the examples are not limited thereto. Absent. In these, use of an organic base is more preferable from viewpoints, such as prevention of circuit wiring corrosion by the ionic impurity in a resin composition. These may be used alone or in combination. The compounding quantity of a basic substance is 0.01-10 weight part with respect to 100 weight part of alkali-soluble resin (The solid content in the case of a solution). More preferably, 0.1 to 5 parts by weight is desirable. If it is less than the lower limit, 50% or more of the carboxyl groups in the alkali-soluble resin are not removed out of the system, which adversely affects the dielectric constant and moisture resistance reliability of the resin layer. On the other hand, when the upper limit is exceeded, the moisture resistance reliability is lowered due to the influence of the remaining basic substance itself.

  The photosensitive material used in the alkali-soluble resin composition of the present invention has a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and among these, a high solubility contrast with a particularly small exposure amount. In order to obtain 1,2-naphthoquinone-2-diazide-5-sulfonic acid or an ester compound of 1,2-naphthoquinone-2-diazide-4-sulfonic acid and a phenol compound is preferable. This photosensitive material functions as a positive photosensitive material that generates a carboxyl group by a photoreaction during exposure by radiation irradiation and increases the solubility of the exposed portion in an alkaline developer. The blending amount of the photosensitive material is preferably 1 to 50 parts by weight, more preferably 2 to 25 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (solid content in the case of a solution). If the amount is less than 1 part by weight, it is difficult to form a pattern of the photosensitive resin composition, and if it exceeds 50 parts by weight, the sensitivity is greatly lowered, which is not preferable. The alkali-soluble photosensitive resin composition used in the present invention can be appropriately blended with a phenol compound, a silane coupling agent, a leveling agent and the like as necessary for the purpose of improving characteristics such as sensitivity.

  As a method for producing a resin layer using the alkali-soluble photosensitive resin composition according to the present invention, for example, after forming a resin layer on a substrate such as glass, a semiconductor element, or a circuit wiring, and performing exposure and development by photolithography A method of performing post-exposure and completing the resin layer by heat curing can be mentioned. Examples of the method for forming the resin layer include a method in which a solution of the photosensitive resin composition is applied onto a substrate by a casting method and then the solvent is removed by drying. The exposure is performed by irradiating the pattern shape with radiation having an energy wavelength that can cause the photosensitive material to react. Specifically, X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used, but those having a wavelength of 200 to 500 nm are desirable. As the developer, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate and aqueous ammonia, aqueous solutions of organic alkalis such as tetramethylammonium hydroxide, ethylamine, triethylamine and triethanolamine, and methanol, An aqueous solution to which an appropriate amount of a water-soluble organic solvent such as alcohol or a surfactant such as ethanol is added can be preferably used.

  Examples of the development method include immersion of the substrate in a developer, paddle development, spray development, ultrasonic development, and the like. The resin pattern formed after development is rinsed. Distilled water is used as the rinse liquid. In the post-exposure, the entire surface of the resin layer after development can be exposed with an exposure machine, a UV conveyor, or the like used for pattern exposure. By this step, unreacted photosensitive groups in the photosensitive material are converted to carboxyl groups, and a resin layer having excellent transparency can be obtained by suppressing light absorption. The resin layer is completed by heat-curing after post-exposure. That is, when the benzocyclobutene structure in the resin reacts by heating, a strong cross-linked structure can be formed and heat resistance can be expressed, and at the same time, the heat is present in the resin and is alkali-soluble during photoprocessing. Carboxyl groups that contributed to expression and carboxyl groups generated from the photosensitive material present in the resin layer by the post-exposure part are removed out of the system by decarboxylation reaction, and the dielectric constant and moisture resistance reliability of the processed resin layer, etc. The greatest feature of the present invention is that it can prevent adverse effects on the reliability of the system. Post-curing can be performed by heating to 100 to 250 ° C. using an oven or a hot plate. Heating is performed in an inert gas atmosphere that does not directly react with an alkali-soluble photosensitive resin composition such as nitrogen or argon. After this step, a resin layer having excellent heat resistance, reliability, electrical characteristics, and transparency can be obtained.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited at all by these Examples.
The obtained compound was subjected to melting point measurement, ¹ H-NMR, ¹³ C ( ¹ H) -NMR, measurement of various spectra of MS and elemental analysis for property evaluation. The measurement conditions for each characteristic were as follows.

Test method (1) Melting point: DSC-200 type differential scanning calorimeter (DSC) manufactured by Seiko Electronics Co., Ltd., 10 ° C./min. It measured by the temperature increase rate of.
(2) Nuclear magnetic resonance spectrum analysis ( ¹ H-NMR, ¹³ C ( ¹ H) -NMR): Measured using JNM-GSX400 type manufactured by JEOL. ¹ H-NMR was measured at a resonance frequency of 400 MHz, and ¹³ C ( ¹ H) -NMR was measured at a resonance frequency of 100 MHz. As a measurement solvent, deuterated acetone CD ₃ COCD ₃ which is a deuterated solvent was used.
(3) Infrared spectroscopic analysis (IR): Measured by the KBr tablet method using a PARAGON 100 model manufactured by PerkinElmer.
(4) Mass spectrometry (MS): Measured by a field desorption (FD) method using a JMS-700 type manufactured by JEOL Ltd.
(5) Elemental analysis: Carbon and hydrogen were measured using a Model 2400 manufactured by PERKIN ELMER.

Example 1
4-Bromobenzocyclobutene (36.6 g, 0.2 mol) and 3-butenoic acid (21.5 g, 0.25 mol) were added to a 200 mL 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirring device. , 1.82 g (0.007 mol) of triphenylphosphine, 25.8 g (0.2 mol, pka = 11.3) of dibutylamine, 0.39 g (0.002 mol) of palladium acetate and N, N-dimethylformamide 75 mL was introduced and heated at 90 ° C. for 5 hours with stirring under a nitrogen stream. After heating, the reaction system was dropped into a 10% aqueous sodium hydroxide solution, unreacted substances were extracted and removed with toluene, 10% hydrochloric acid was dropped, and the precipitate obtained by filtration was recrystallized from methanol, Was dried in vacuo to give 35.2 g of 1- (benzocyclobuten-4-yl) -3-butenoic acid of the formula (11) as white crystals (yield 93.5%).

The spectrum data of the obtained 1- (benzocyclobuten-4-yl) -3-butenoic acid are shown below. These data support that the obtained compound is the target product.

[1- (Benzocyclobuten-4-yl) -3-butenoic acid (C ₁₂ H ₁₂ O ₂ )]
Appearance: Pale yellow solid melting point: 187 ° C (DSC, 10 ° C / min)
¹ H-NMR: (400 MHz, CD ₃ OCD ₃ -d ₆ ): δ 7.38 (d, 1H), 7.22 (d, 1H), 7.06 (d, 1H), 6.07 (s, 2H), 3.15 (s, 4H), 2.55 (s, 1H), 2.53 (s, 2H)

¹³ C ( ¹ H) -NMR: (100 MHz, DMSO-d ₆ ): δ 139.51, 138.82, 131.18, 128.45, 127.70, 125.53, 123.26, 120.18, 76.03, 38.35, 26.46, 26.07

IR (KBr, cm ⁻¹ ): 618, 713, 769, 829, 867, 924, 1143, 1219, 1258, 1288, 1351, 1372, 1443, 1478, 1504, 1538, 1556, 1613, 1681, 1693, 2350 , 2541, 1925

MS (FD) (m / z): 188.1 (M ^<+> )
Elemental analysis: Theoretical value C: 76.57% H: 6.43%
Actual value C: 76.50% H: 6.39%

Example 2
Similar to Example 1, substituting 14.2 g (0.2 mol, pka = 11.2) of pyrrolidine for 25.8 g (0.2 mol, pka = 11.3) of dibutylamine of Example 1. Reaction was performed to obtain 34.8 g (yield 92.4%) of white crystals. The same measurement as in Example 1 was performed, and it was confirmed that the compound was the same as the formula (11).

Example 3
In a 100 ml four-necked flask equipped with a thermometer, a condenser tube, a nitrogen inlet tube, and a stirrer, 17.6 g (0.093 mol) of the above-obtained (11), 1,3-bis (2-bicyclo [ 4.2.0] octa-1,3,5-trien-3-ylethenyl) -1,1,3,3-tetramethyldisiloxane 11.8 g (0.030 mol) and dipropylene glycol methyl ether 88 .2 g was introduced, and the mixture was reacted by heating at 160 ° C. for 50 hours while stirring in a nitrogen stream to obtain a resin solution (2) (resin content: 23.8%). The carboxyl group equivalent with respect to the solid content of the resin obtained by titration of the solution was 320 g / mol. 20 g of the obtained resin solution (2), 0.05 g of triphenylphosphine and 0.5 g of the photosensitive material represented by the formula (12) were mixed to obtain a uniform photosensitive resin composition (4).

The obtained photosensitive resin composition (4) was applied onto a glass substrate with a spin coater and dried on a hot plate at 100 ° C. for 10 minutes to form a resin layer having a thickness of 2 μm. Using a parallel exposure machine (light source: high-pressure mercury lamp) through a mask, exposure was performed through a glass mask at an exposure intensity of 25 mW / cm ² for 15 seconds. Thereafter, the resin layer was immersed and developed in an aqueous 2.38% tetramethylammonium hydroxide solution for 30 seconds, whereby the resin layer in the exposed area was dissolved, and a patterned resin layer could be obtained. Thereafter, the entire resin layer was post-exposed for 400 seconds at an exposure intensity of 25 mW / cm ² using the parallel exposure machine used for exposure, and then heated at 240 ° C. under a nitrogen stream using a hot air circulation dryer. Heat curing was performed for 1 hour. Separately, the infrared absorption spectrum of (4) before and after heat curing was measured with an FT-IR spectrometer (PARAGON100 type, manufactured by PerkinElmer), and was derived from the carboxyl group hydroxyl group observed at 2500 to 3500 cm ^−1. It was confirmed that the absorption decreased by 78% by heat curing.

About the obtained resin layer, the following characteristics were measured.
Transmittance: As a measure of transparency, the light transmittance at a wavelength of 400 nm was measured using a spectrophotometer (UV-160, manufactured by Shimadzu Corporation) for the glass substrate with a resin layer. The transmittance was 99%, indicating that the transparency was good.
Water absorption: The resin layer peeled from the glass substrate with the resin layer was immersed in water at 23 ° C. for 24 hours, and the weight change rate before and after immersion was measured. The weight change rate was as low as 1.2%.
Dielectric constant: Measured according to MIL-P-55617, a value of 3.0 was obtained.
Thermal weight reduction start temperature: Using a differential thermal balance (TG / DTA 6200 type, manufactured by Seiko Instruments Inc.), the weight reduction start temperature was measured at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere to reduce the weight. The temperature was found to be 290 ° C.
The measurement results showed good values for all items.

Comparative Example 1
Similar to Example 1, substituting 20.2 g (0.2 mol, pka = 10.8) of triethylamine for 25.8 g (0.2 mol, pka = 11.3) of dibutylamine of Example 1. Although the reaction was performed, only 4.5 g (yield 11.9%) of crystals was obtained.

Comparative Example 2
Similar to Example 1 except that 15.8 g of pyridine (0.2 mol, pka = 5.4) was used instead of 25.8 g (0.2 mol, pka = 11.3) of dibutylamine of Example 1. The reaction was carried out, but no crystals were obtained.

Comparative Example 3
Using 18.0 g (0.25 mol) of acrylic acid instead of 21.5 g (0.25 mol) of 3-butenoic acid of Example 1, the reaction was carried out in the same manner as in Example 1, and the formula was a white crystal 32.3 g of 1- (benzocyclobuten-4-yl) -2-butenoic acid of (13) was obtained (yield 92.8%).

The same reaction as in Example 3 was carried out using 16.2 g (0.093 mol) of formula (13) obtained above instead of 17.6 g (0.093 mol) of formula (11) of Example 3. To obtain a resin solution. In the same manner as in Example 3, the photosensitive resin composition was prepared, applied, and heat-cured to examine the characteristics.
About the obtained resin layer, the following characteristics were measured.
Transmittance: As a measure of transparency, the light transmittance at a wavelength of 400 nm was measured using a spectrophotometer (UV-160, manufactured by Shimadzu Corporation) for the glass substrate with a resin layer. The transmittance was found to be 87%.
Water absorption: The resin layer peeled from the glass substrate with the resin layer was immersed in water at 23 ° C. for 24 hours, and the weight change rate before and after immersion was measured. The weight change rate was as high as 2.8%.
Dielectric constant: Measured according to MIL-P-55617 and obtained a value of 3.1.
Thermal weight reduction start temperature: Using a differential thermal balance (TG / DTA 6200 type, manufactured by Seiko Instruments Inc.), the weight reduction start temperature was measured at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere to reduce the weight. The temperature was found to be 210 ° C.
The measurement results showed values inferior to Example 3 for all items.

The present invention provides an alkali-soluble resin usable as an insulating film for a display element, a semiconductor or printed wiring, a protective film or an interlayer insulating film, and a carboxylic acid useful as a raw material for a photosensitive resin composition. A method and an alkali-soluble resin are provided.
By using the alkali-soluble photosensitive resin composition using the raw material of the present invention, pattern formation is easy in a photolithography process using an alkaline aqueous solution, high reliability such as high heat resistance and moisture resistance reliability, and further high transparency, An insulating resin layer having excellent characteristics with a low dielectric constant can be obtained. This insulating resin layer can be used for an insulating film for a display element, a semiconductor or a printed wiring, a protective film or an interlayer insulating film material, and is industrially useful.

Claims (3)

An aromatic carboxylic acid represented by general formula (3), wherein a compound represented by formula (1) and a compound represented by general formula (2) are reacted in the presence of a palladium catalyst complex and a base. Manufacturing method.
R ₁ is a hydrogen atom, —CO—R ₂ or —SO ₂ —R ₂ .
n is an integer of 1 or more, and R ₁ is a hydrogen atom, —CO—R ₂ or —SO ₂ —R ₂ . The method for producing an aromatic carboxylic acid according to claim 1, wherein the base has a pka of 11 or more. A resin obtained by heating and reacting a compound represented by the general formula (3) and a compound having two or more benzocyclobutene structures in one molecule at 100 to 200 ° C., and having a carboxyl group equivalent of 400 g / mol or less. An alkali-soluble resin composition characterized by being.