JP4277616B2 - Alkali-soluble photosensitive resin composition and method for forming resin layer - Google Patents

Description

  The present invention relates to an alkali-soluble photosensitive fat composition and a method for forming a resin layer using the same.

  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 and processed with 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 in order to develop alkali developability may deteriorate the characteristics such as the 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 and has excellent characteristics such as high heat resistance, high reliability, high transparency, and low dielectric constant.
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 provides an alkali-soluble photosensitive resin composition having excellent properties, high transparency, and low dielectric constant, and a method for forming a resin layer using the same.

（Ｘは酸性基あるいは、酸性基を有する１価の有機基。）
［３］第［１］または［２］項記載のアルカリ可溶性感光性樹脂組成物を用いて、基板上に前記感光性樹脂組成物の樹脂層を形成する工程、パターン露光を行う工程、アルカリ水溶液による現像で樹脂層をパターン加工する工程、樹脂層全面に後露光を行う工程及び樹脂層を不活性気体中、１００〜２５０℃で加熱する工程を含むことを特徴とする樹脂層の形成方法、
［４］第［１］または［２］項記載のアルカリ可溶性感光性樹脂組成物を用いて、ガラス基板上に感光性樹脂組成物の樹脂層を形成したことを特徴とする樹脂付きガラス基板。
である。

The present invention
[1] (A) A resin obtained by heating and reacting a compound having a benzocyclobutene structure and a carboxyl group in one molecule and a compound having two or more benzocyclobutene structures in one molecule at 100 to 200 ° C. The compound having a benzocyclobutene structure and a carboxyl group in one molecule uses a Heck reaction from a compound having a benzocyclobutene structure and a halogen atom and a compound having a carboxyl group and a carbon-carbon double bond. A compound having two or more benzocyclobutene structures in one molecule and a compound having two or more benzocyclobutene structures in one molecule and having a C═C bond or C═O. An alkali-soluble resin having a carboxyl group equivalent of 400 g / mol or less, (B) a compound having an epoxy group, (C) the alkali It contains 0.01 to 10 parts by weight of a basic substance and (D) a photosensitive material having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure with respect to 100 parts by weight of a soluble resin. An alkali-soluble photosensitive resin composition,
[2] The alkali-soluble photosensitivity according to item [1], wherein the compound having a benzocyclobutene structure and a carboxyl group in one molecule is a compound having a structure represented by the general formula (3) Resin composition.

(X is an acidic group or a monovalent organic group having an acidic group.)
[3] A step of forming a resin layer of the photosensitive resin composition on a substrate using the alkali-soluble photosensitive resin composition according to the item [1] or [2], a step of pattern exposure, an alkaline aqueous solution A method of forming a resin layer, comprising: patterning the resin layer by development, post-exposure on the entire surface of the resin layer, and heating the resin layer at 100 to 250 ° C. in an inert gas;
[4] A resin-coated glass substrate, wherein a resin layer of a photosensitive resin composition is formed on a glass substrate using the alkali-soluble photosensitive resin composition according to [1] or [2].
It is.

  By using the alkali-soluble photosensitive resin composition of the present invention, pattern formation is easy in a photolithography process using an aqueous alkali solution, high reliability such as high heat resistance and moisture resistance reliability, higher transparency, and low dielectric constant. An insulating resin layer having excellent characteristics 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, a planarizing film, an interlayer insulating film material, and the like, and is industrially useful.

The alkali-soluble resin used in the present invention is a reaction in which a compound having a benzocyclobutene structure and a carboxyl group in one molecule and a compound having two or more benzocyclobutene structures in one molecule are heated at 100 to 200 ° C. Resin having a carboxyl group equivalent of 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 in development as described later, tetramethylammonium hydroxide and ethylamine are used. It becomes soluble in an aqueous solution of an organic alkali such as triethylamine or triethanolamine, and an aqueous alkaline solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as an alcohol such as methanol or ethanol. 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 compound having a benzocyclobutene structure and a carboxyl group in one molecule used in the present invention includes, for example, a compound having a benzocyclobutene structure and a halogen atom, and a compound having a carboxyl group and a carbon-carbon double bond. Obtained by heating reaction. Although the manufacturing method is not particularly limited, for example, Heck reaction can be used. 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 the general formula (1) and the compound represented by the formula (2) are stirred in an inert atmosphere in the presence of a solvent, a palladium catalyst, and an acid scavenger such as trimethylamine. By carrying out the heating reaction, a compound having a benzocyclobutene structure and a carboxyl group in one molecule represented by the general formula (3) can be obtained. Specific examples of such compounds include compounds represented by formula (4), formula (5), formula (6), and formula (7).

  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 production of the alkali-soluble resin used in the present invention comprises a compound having a benzocyclobutene structure and a carboxyl group in one molecule and a compound having two or more benzocyclobutene structures in one molecule, without solvent or in a solvent. And heating at 100 to 200 ° C. When the temperature is lower than 100 ° C., the high molecular weight reaction does not occur sufficiently and the film-forming property is inferior. 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. Exceeding 100 hours is not preferable because the resulting resin has a high molecular weight and three-dimensionalization progresses, resulting in a decrease in alkali solubility. The molecular weight of these alkali-soluble resins can be measured as a polystyrene-equivalent 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, when the resin is produced, by changing the charging ratio of the compound having a benzocyclobutene structure and a carboxyl group in one molecule and the compound having two or more benzocyclobutene structures in one molecule, The carboxyl group equivalent can be controlled. 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 210 ° C. for 60 minutes, and the ratio of the solid content obtained to the weight of the original resin solution I can know.

  Examples of the polyfunctional epoxy compound used in the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, silicone modified epoxy resin, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxyl. Examples thereof include alicyclic epoxy resins such as a rate. Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, silicone modified epoxy resin, alicyclic epoxy resin, and the like are desirable from the viewpoint of transparency, heat resistance, compatibility with other components, and the like.

  The basic substance used in the present invention is used for the purpose of accelerating the ring-opening polyaddition reaction between the carboxyl group in the alkali-soluble resin and the polyfunctional epoxy compound in the heat curing after photoprocessing. The addition amount of the basic substance is desirably 0.01 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the alkali-soluble resin. Examples of such basic substances include 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 the like can be mentioned, but are not limited thereto. 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 photosensitive resin composition of the present invention has a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and among these, particularly high solubility at a small exposure dose. In order to obtain this contrast, 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. 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 film using the alkali-soluble photosensitive resin composition according to the present invention, this resin layer is formed on a substrate, exposed and developed by a photolithography process, post-exposed, and post-cured. The method of completing a resin layer can be mentioned. The resin layer can be formed by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, scan coating, slitting, or a combination thereof on a substrate. Subsequent solvent removal by drying can be mentioned. The exposure is performed by irradiating the pattern shape with radiation light having a wavelength of energy at which the photoacid generator can cause a reaction. Applicable exposure apparatuses include a parallel exposure apparatus, a contact exposure apparatus, a mask aligner, a stepper, and a drawing apparatus using a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, a KrF laser as a light source. As the developer, for example, an aqueous alkali solution such as tetramethylammonium hydroxide, sodium carbonate, triethanolamine, sodium carbonate, or sodium hydroxide can be 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. The carboxyl group that contributed to the expression, disappeared by the ring-opening polyaddition reaction with the epoxy group in the polyfunctional epoxy compound, the carboxyl group generated from the photosensitive material present in the resin layer by the post-exposure part, after processing It is a feature of the present invention that adverse effects on the reliability of the resin layer, such as the dielectric constant and moisture resistance reliability, can be prevented. 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.
Example 1
4-bromobenzocyclobutene 36.6 g (0.2 mol), acrylic acid 18 g (0.25 mol), triphenylphosphine in a 100 ml four-necked flask equipped with a thermometer, a condenser tube, a nitrogen inlet tube, and a stirrer 0.18 g, 20.2 g (0.2 mol) of triethylamine, 0.39 g (0.002 mol) of palladium acetate and 75 mL of N, N-dimethylformamide were introduced and heated at 90 ° C. for 5 hours with stirring under a nitrogen stream. did. After heating, the reaction system was dropped into a 10% aqueous sodium hydroxide solution, and unreacted substances were extracted and removed with toluene. After 10% hydrochloric acid was added dropwise, the mixture was cooled to 10 ° C. or lower, and the filtrate was filtered from the precipitated white crystals. Separately, by vacuum drying at room temperature, 2- (bicyclo [4.2.0] octa-1,3,5-trien-3-yl) acrylic acid (1) of formula (4) was obtained.

Next, (1) 12.7 g (0.073 mol), 1,3-bis (2-bicyclo [1]) obtained in a 100 mL 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device were used. 4.2.0] Octa-1,3,5-trien-3-ylethenyl) -1,1,3,3-tetramethyldisiloxane 9.5 g (0.024 mol) and dipropylene glycol methyl ether 66 mL Was heated at 150 ° C. for 50 hours with stirring under a nitrogen stream to obtain a resin solution (2) (resin content: 23.0%). The carboxyl group equivalent with respect to solid content of the obtained resin was 304 g / mol.
(2) 20 g obtained, Celoxide 2021 (Daicel Chemical Industries, Ltd., alicyclic epoxy, epoxy equivalent: about 126 g / mol) 0.95 g, triphenylphosphine 0.1 g and the formula (11) 1.0 g of a photosensitive material was mixed to obtain a uniform resin composition solution (3).

(3) was coated on a glass substrate with a spin coater and dried on a hot plate at 100 ° C. for 10 minutes to form a resin film having a thickness of about 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 film was immersed and developed in an aqueous 2.35% tetramethylammonium hydroxide solution for 30 seconds, whereby the resin in the exposed area was dissolved and a patterned resin film could be obtained. Thereafter, the entire resin film was subjected to post-exposure for 40 seconds at an exposure intensity of 25 mW / cm ² using the parallel exposure machine used at the time of exposure, and then at a maximum of 240 ° C. under a nitrogen stream using a hot air circulation dryer. Heat curing was performed for 1 hour.

The obtained resin film was measured for the following characteristics.
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. (unit,%). The higher the transmittance, the better the transparency.
Water absorption: The resin layer peeled from the glass substrate with a resin layer was immersed in water at 23 ° C. for 24 hours, and the weight change rate before and after immersion was measured. (unit,%)
Dielectric constant: measured according to MIL-P-55617.
Thermogravimetric decrease start temperature: Using a differential thermal balance (TG / DTA 6200 type, manufactured by Seiko Instruments Inc.), the weight decrease start temperature was measured at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere (unit, ° C).
The measurement results are shown in Table 1. The resin layer obtained from Table 1 showed good values for all items.

Example 2
4-bromobenzocyclobutene 36.6 g (0.2 mol), 1,3-butadiene-1-carboxylic acid 28 g (0) were added to a 100 ml four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device. .25 mol), 0.18 g of triphenylphosphine, 20.2 g (0.2 mol) of triethylamine, 0.39 g (0.002 mol) of palladium acetate and 75 mL of N, N-dimethylformamide were introduced and stirred under a nitrogen stream. The mixture was heated at 90 ° C. for 5 hours. After heating, the reaction system was dropped into a 10% aqueous sodium hydroxide solution, and unreacted substances were extracted and removed with toluene. After 10% hydrochloric acid was added dropwise, the mixture was cooled to 10 ° C. or lower, and the filtrate was filtered from the precipitated white crystals. Separately, by vacuum drying at room temperature, 4- (bicyclo [4.2.0] octa-1,3,5-trien-3-yl) -1,3-butadiene-1-carboxylic acid of formula (7) The acid (5) was obtained.
Next, (5) 28.2 g (0.14 mol) obtained in a 100 mL 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device, 1,3-bis (2-bicyclo [ 4.2.0] octa-1,3,5-trien-3-ylethenyl) -1,1,3,3-tetramethyldisiloxane 13.8 g (0.035 mol) and dipropylene glycol methyl ether 126 mL Was heated at 150 ° C. for 50 hours with stirring under a nitrogen stream to obtain a resin solution (6) (resin content: 24.0%). The hydroxyl group equivalent with respect to solid content of the obtained resin was 298 g / mol.
20 g obtained (6), Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy, epoxy equivalent: about 126 g / mol) 0.95 g, triphenylphosphine 0.1 g and formula (11) 1.0 g of photosensitive material was mixed to obtain a uniform resin composition solution (7). (7) A resin film was formed on the glass substrate in the same manner as in Example 1, and exposure, development, post-exposure and thermosetting were performed. The transparency, water absorption, dielectric constant, and thermogravimetric decrease starting temperature of the obtained resin film were measured in the same manner as in Example 1, and the results are also shown in Table 1. From Table 1, the obtained resin film showed a good value for any of the above items.

Comparative Example 1
20 g of (2) obtained in Example 1, 0.1 g of triphenylphosphine, and 1.0 g of the photosensitive material represented by the formula (11) were mixed to obtain a uniform resin composition solution (8). (8) A resin film was formed on a glass substrate in the same manner as in Example 1, and exposure, development, post-exposure and thermosetting were performed. The transparency, water absorption, dielectric constant, and thermogravimetric decrease starting temperature of the obtained resin film were measured in the same manner as in Example 1, and the results are also shown in Table 1. From Table 1, the water absorption and dielectric constant of the obtained resin were inferior to those obtained in the examples.

Comparative Example 2
(1) 7.5 g (0.037 mol), 1,3-bis (2-bicyclo) obtained in Example 1 in a 100 mL 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device [4.2.0] octa-1,3,5-trien-3-ylethenyl) -1,1,3,3-tetramethyldisiloxane 14.5 g (0.037 mol) and acetic acid dipropylene glycol methyl ether 66 mL was introduced and heated at 150 ° C. for 50 hours with stirring under a nitrogen stream to obtain a resin solution (9) (resin content: 23.0%). The carboxyl group equivalent with respect to solid content of the obtained resin was 591 g / mol.
20 g obtained (9), Celoxide 2021 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy, epoxy equivalent: about 126 g / mol) 0.95 g, triphenylphosphine 0.1 g and formula (11) 1.0 g of photosensitive material was mixed to obtain a uniform resin composition solution (10).
In (10), a resin film was formed on the glass substrate in the same manner as in Example 1, and exposure and development were performed. However, neither the exposed or unexposed resin was dissolved in the developer.

The present invention relates to an alkali-soluble resin, a photosensitive resin composition, and a resin layer using the same, which 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. A forming method is provided.
By using the alkali-soluble photosensitive resin composition of the present invention, pattern formation is easy in a photolithography process using an aqueous alkali solution, high reliability such as high heat resistance and moisture resistance reliability, higher transparency, and low dielectric constant. An insulating resin layer having excellent characteristics 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, a planarizing film, an interlayer insulating film material, and the like, and is industrially useful.

Claims (4)

(A) a resin obtained by heating and reacting a compound having a benzocyclobutene structure and a carboxyl group in one molecule and a compound having two or more benzocyclobutene structures in one molecule at 100 to 200 ° C .;
A compound having a benzocyclobutene structure and a carboxyl group in one molecule is obtained using a Heck reaction from a compound having a benzocyclobutene structure and a halogen atom and a compound having a carboxyl group and a carbon-carbon double bond. A compound
The compound having two or more benzocyclobutene structures in one molecule is a compound having two or more benzocyclobutene structures in one molecule and C═C or C═O.
An alkali-soluble resin having a carboxyl group equivalent of 400 g / mol or less, (B) a compound having an epoxy group, (C) 0.01 to 10 parts by weight of a basic substance with respect to 100 parts by weight of the alkali-soluble resin, and ( D) An alkali-soluble photosensitive resin composition comprising a photosensitive material having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure. 2. The alkali-soluble photosensitive resin composition according to claim 1, wherein the compound having a benzocyclobutene structure and a carboxyl group in one molecule is a compound having a structure represented by the general formula (3).

(X is an acidic group or a monovalent organic group having an acidic group.)   A step of forming a resin layer of the photosensitive resin composition on a substrate using the alkali-soluble photosensitive resin composition according to claim 1, a step of performing pattern exposure, and a patterning of the resin layer by development with an aqueous alkali solution A method for forming a resin layer, comprising a step of processing, a step of performing post-exposure on the entire surface of the resin layer, and a step of heating the resin layer at 100 to 250 ° C. in an inert gas.   A glass substrate with a resin, wherein a resin layer of the photosensitive resin composition is formed on a glass substrate using the alkali-soluble photosensitive resin composition according to claim 1.