JP4341336B2 - Photosensitive resin composition and method for forming resin layer - Google Patents

Description

  The present invention relates to a 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. In the former, a positive pattern is obtained, and in the latter, a negative pattern is obtained. In the past, organic solvents were mainly used for dissolution of the resin layer by development, etc., but in order to ensure a good working environment, dissolution processing can be performed with an aqueous solution of alkali or the like, and a fine pattern can be formed. A positive photosensitive resin composition is required.

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). In these photosensitive resins, a diazoquinone compound is used as a photosensitive material in order to obtain a positive pattern capable of alkali development. The diazoquinone compound undergoes a chemical change upon exposure and becomes soluble in an alkaline aqueous solution. However, in the unexposed part (unexposed part), since the absorption with respect to the light itself is large, the thin film also exhibits a yellow color and the transparency is lowered. In addition, since diazoquinone exhibits fading when exposed to light, there is a problem that even if the entire surface of the substrate is exposed after development, the number of steps increases and throughput decreases.
Further, in the case of a carboxyl group introduced to develop alkali developability, it does not interact with the diazoquinone compound, and further, the solubility in an alkaline aqueous solution is much higher than that of a phenolic hydroxyl group. Thus, there is a problem that the dissolution inhibiting ability is not exhibited, the target film thickness cannot be obtained, and the pattern formation itself becomes difficult.
Therefore, a novel 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 is desired.
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, a planarizing film, or an interlayer insulating film material for display elements, semiconductors, printed wirings, etc., and can easily form a pattern, and has high heat resistance and moisture resistance reliability. The present invention provides a photosensitive resin composition having excellent properties such as high reliability, higher transparency, and low dielectric constant, and a method for forming a resin layer using the same.

The present invention
[1] Obtained by heating and reacting at least one compound represented by the general formulas (1) to (4) and a compound having two or more benzocyclobutene structures in one molecule at 100 to 200 ° C., It is a resin having a hydroxyl group equivalent of 400 g / mol or less , and further, 5 to 80% of hydrogen in all hydroxyl groups contained in the resin is an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxy having 2 to 20 carbon atoms. A resin substituted with a group selected from an alkyl group, an alkyl-substituted silyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, and a tetrahydrofuranyl group, and (B) a compound that generates an acid by light. A photosensitive resin composition.

（Ｒ₁，Ｒ₃は水素原子または炭素数６以下のアルキル基であり、Ｒ₂，Ｒ₄は炭素数６以下のアルキル基または単結合である。Ｒ₅は少なくとも水酸基を１個以上有する２価の環状化合物基である。Ｒ₆は ―ＣＨ₂―または―ＣＯ―である。ｍは０〜２の整数、ｎは１〜３の整数、ｐは０〜２の整数、ｑは１〜３の整数である。）

(R ₁ and R ₃ are a hydrogen atom or an alkyl group having 6 or less carbon atoms, and R ₂ and R ₄ are an alkyl group or a single bond having 6 or less carbon atoms. R ₅ is a 2 having at least one hydroxyl group. R ₆ is —CH ₂ — or —CO—, m is an integer of 0 to 2, n is an integer of 1 to 3, p is an integer of 0 to 2, and q is 1 to 2. It is an integer of 3.)

[2] Using the photosensitive resin composition according to item [1], a step of forming a resin layer of the photosensitive resin composition on a substrate, a step of pattern exposure, a step of heating after exposure, an alkali A process for patterning the resin layer by development with an aqueous solution, and a method for forming the resin layer, the method comprising heating the resin layer at 100 to 250 ° C. in an inert gas;
It is.

  By using the photosensitive resin composition 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 excellent transparency and low dielectric constant. An insulating resin layer having 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 resin used in the present invention is a reaction in which at least one compound represented by the general formulas (1) to (4) and a compound having two or more benzocyclobutene structures in one molecule are heated at 100 to 200 ° C. The hydroxyl group equivalent is 400 g / mol or less, and 5 to 80% of hydrogen in all hydroxyl groups is an alkoxycarbonyl group having 2 to 20 carbon atoms and 2 to 20 carbon atoms. It is substituted with a group selected from an alkoxyalkyl group, an alkyl-substituted silyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, and a tetrahydrofuranyl group.

  As long as the hydroxyl group equivalent is 400 g / mol or less, although not particularly limited, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, and aqueous ammonia used in development as described later, tetramethylammonium hydroxide and ethylamine, Protective groups described below were eliminated in aqueous solutions of organic alkalis such as triethylamine and triethanolamine, and alkaline aqueous solutions to which water-soluble organic solvents and surfactants such as alcohols such as methanol and ethanol were added. The alkali-soluble resin becomes soluble. When the hydroxyl 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 hydroxyl groups in the resin can be measured by titration of the resin solution using a standard alkaline solution.

  In order to obtain a photosensitive resin capable of positive pattern processing, 5 to 80% of hydrogen in all hydroxyl groups in the resin is composed of an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxy having 2 to 20 carbon atoms. It is necessary to be substituted with a group selected from an alkyl group, an alkyl-substituted silyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, and a tetrahydrofuranyl group, which may be the same or different. If it is less than 5%, the pattern processing becomes difficult because the unexposed part cannot have sufficient resistance to the alkaline aqueous solution as the developer, and if it exceeds 80%, the exposed part (exposed part) Not only does the solubility become extremely slow and the sensitivity decreases, but also resin residue (scum) tends to be generated after development.

The compound represented by the general formula (1) used in the present invention is obtained, for example, by subjecting a compound represented by the general formula (5) and a compound represented by the formula (6) to a heating reaction. Although the manufacturing method of the compound shown by General formula (1) is not specifically 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, a compound represented by the general formula (5) and a compound represented by the formula (6) are stirred 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 heating reaction.

（Ｒ₇はハロゲン原子である。）

(R ₇ is a halogen atom.)

  The compound represented by the general formula (2) used in the present invention is, for example, an activity obtained by reacting a compound represented by the general formula (7) with 1-hydroxy-1,2,3-benzotriazole in advance. It can be easily obtained by heating and reacting an ester type carboxylic acid derivative and a compound selected from bis (aminophenol) having a structure represented by the general formula (8) in an inert atmosphere.

（Ｒ₈は ２価の有機基である。）

(R ₈ is a divalent organic group.)

For example, Friedel-Crafts reaction can be used as the method for producing the compound represented by the general formula (3) used in the present invention. Specifically, the compound represented by the general formula (9) and the compound having the structure represented by the general formula (10) are cooled and reacted in the presence of a Lewis acid such as aluminum chloride (■). It is done.

  The production of the compound represented by the general formula (4) used in the present invention can be obtained, for example, by using the method described in US Pat. No. 5,227,536.

  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 (11), formula (12), and formula (13). It is not limited. Of these, the compound represented by the general formula (11) is preferable from the viewpoint of the mechanical properties of the heat-cured resin.

  The resin used in the present invention is prepared by using at least one compound represented by the general formulas (1) to (4) and a compound having two or more benzocyclobutene structures in one molecule without solvent or in a solvent. After heating at 100 to 200 ° C., a predetermined proportion of the hydroxyl group hydrogen is replaced with a protecting group selected from an alkoxycarbonyl group, an alkoxyalkyl group, an alkyl-substituted silyl group, a tetrahydropyranyl group, and a tetrahydrofuranyl group. do it. 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 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 1000 or more as the weight average molecular weight. It is desirable that it is 30000 or less.

  Further, during the production of this resin, it is obtained by changing the charging ratio of at least one compound represented by the general formulas (1) to (4) and a compound having two or more benzocyclobutene structures in one molecule. The hydroxyl equivalent of the resulting resin can be controlled. Solvents when the reaction is carried out in a solvent include mesitylene, γ-butyrolactone, dimethyl sulfoxide, cycloheptanone, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, diethylene glycol Examples thereof include propylene glycol monomethyl ether acetate and ethyl lactate, and 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 is dissolved in a solvent as described above, and after a protective group is added, a photosensitive resin composition may be produced. When obtained as a resin solution, the concentration of the resin in the solution can be known as the ratio of the weight of the solid content obtained and the weight of the original resin solution after heating a certain weight of the resin solution at 210 ° C. for 60 minutes. .

  The obtained resin is applied to a substrate to form a resin layer as a photosensitive resin composition containing (A) the above-described resin and (B) a compound that generates an acid by light, and exposure. Then, after exposure, development, rinsing, and heat curing in a heating temperature range of 100 to 250 ° C.

  The compound (B) that generates an acid by light used in the photosensitive resin composition of the present invention is described in Photograph. Sci. Eng. , 18, p387 (1974), CHEMTECH, Oct. p624 (1980), Polym. Mater. Sci. Eng. 72, p406 (1995), Macromol. Chem. Rapid Commun. 14, p203 (1993), J.M. Photopolym. Sci. Technol. , 6, p67 (1993), Macromolecules, 21, p2001 (1988), Chem. Mater. 3, p462 (1991), Proc. 2-nitrobenzyl esters described in SPIE, 1086, 2 (1989); Photopolym. Sci. Technol. , 2, p429 (1989), Proc. SPIE, 1262, p575 (1990) described N-iminosulfonates, Polym. Mat. Sci. Eng. , 61, 269 (1989), naphthoquinonediazide-4-sulfonic acid esters; Photopolym. Sci. Technol. 4, p389 (1991), Proc. And halogen compounds described in SPIE, 2195, p173 (1994). These may be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention is an acid labile group that decomposes in the presence of an acid and increases the solubility in an alkaline aqueous solution as a developer in order to improve the dissolution contrast between the exposed and unexposed areas. A compound protected with can also be added. As a result, the resistance to alkaline aqueous solution is improved in the unexposed area, and the hydroxyl or carboxyl group is regenerated and dissolved in the exposed area by elimination of the acid labile group by the action of the catalytic acid generated from the photoacid generator. Encourage promoting action.

  As a compound protected with an acid labile group, the hydroxyl group of the phenol compound is an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkoxycarbonylmethyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, carbon A compound protected by a substituent selected from an alkyl-substituted silyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group and a tetrahydrofuranyl group, or a carboxyl group of a compound containing a carboxyl group, an alkyl group having 2 to 20 carbon atoms, A compound protected with a tetrahydropyranyl group. Specific examples include the following, but are not limited thereto.

  The photosensitive resin composition of the present invention can be blended with a crosslinking material for the purpose of improving heat resistance and moisture resistance reliability by reacting with a hydroxyl group in the resin for the purpose of further high heat resistance and high reliability. . Examples of the crosslinking material include polyfunctional epoxy compounds, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, silicone modified epoxy resin, 3,4-epoxycyclohexylmethyl-3,4-epoxy. Examples thereof include alicyclic epoxy resins such as cyclohexanecarboxylate.

Furthermore, for the purpose of improving the mechanical properties of the resin after heat curing, a crosslinking material such as a polyfunctional acrylic compound, a polyfunctional methacrylic compound, a polyfunctional maleimide compound, or a polyfunctional ethynyl compound can be added. These may be used alone or in combination.
Further, in order to efficiently react these crosslinking materials, imidazole derivatives, 1-hydroxyethyl-2-alkylimidazolines, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5]. , 4,0] -7-undecene, triethanolamine, triphenylphosphine, and other basic substances can be added.

  The photosensitive resin composition used for this invention can mix | blend a phenol compound, a silane coupling agent, a leveling agent, etc. suitably as needed for the purpose of characteristic improvement, such as a sensitivity.

As a method for producing a resin layer using the photosensitive resin composition according to the present invention, for example, a resin layer is formed on a substrate such as glass, a semiconductor element, or a circuit wiring, and exposure, post-exposure heating, and development are performed by photolithography. Thereafter, a method of completing the resin layer by heat curing 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, casting, or a combination thereof. A method of removing the solvent by drying after applying the solution onto the substrate can be mentioned. The exposure is performed by irradiating the pattern shape with radiation having a wavelength of energy at which the compound capable of generating an acid by the light can cause a reaction. 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. The post-exposure heating is performed using an oven or a hot plate. By this post-exposure heating, (B) the acid generated from the compound that generates an acid by light diffuses in the exposed area, and (A) the protective group in the resin is eliminated by a catalytic reaction, and the hydroxyl group is regenerated to develop. It becomes soluble in an alkaline aqueous solution, and a positive pattern can be formed.

  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. Further, (B) when the transparency of the resin layer is significantly lowered by light absorption by a compound that generates an acid by light, a post-exposure step can be added after development if necessary. 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, (B) a compound that generates an acid by light is decomposed, and a resin layer having further 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 is formed and heat resistance can be expressed. Heat 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 the 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 (18.3 g, 0.10 mol) and 4-allyl-1,2-dimethoxybenzene (22.3 g) were added to a 200 mL 4-neck flask equipped with a thermometer, a condenser tube, a nitrogen inlet tube, and a stirring device. (0.13 mol), 1.82 g (0.007 mol) of triphenylphosphine, 20.2 g (0.2 mol) of triethylamine, 0.39 g (0.002 mol) of palladium acetate and 55 mL of N, N-dimethylformamide And heated at 90 ° C. for 6 hours with stirring under a nitrogen stream. After heating, the mixture was filtered with a filter and evaporated under reduced pressure to obtain a crude product.

10.0 g (0.036 mol) of this crude product and 5.2 g (0.039 mol) of aluminum chloride (■) in a 200 mL 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device Then, 100 g of ethyl acetate was introduced, and 11.3 g (0.14 mol) of pyridine was slowly added dropwise over 1 hour while keeping the system at 40 ° C. or lower. Then, it was made to react at 50 degreeC for 24 hours. The obtained reaction system was dropped into a 10% aqueous sodium hydroxide solution, and only the aqueous layer was extracted. Then, a 10% aqueous hydrochloric acid solution was dropped until the pH was 3 or less, and the precipitate obtained by filtration was added with methanol. Recrystallization and vacuum drying at room temperature gave a compound (A-1) represented by the formula (14) as white crystals.

Next, in a 200 ml four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device, (A-1) 10.7 g (0.043 mol) obtained in the above, 1,3-bis 2.9 g (0.008 mol) of (2-bicyclo [4.2.0] octa-1,3,5-trien-3-ylethenyl) -1,1,3,3-tetramethyldisiloxane and diacetate 40.9 g of propylene glycol methyl ether was introduced, and the resin solution (A-2) (resin content: 23.2%) was obtained by heating and reacting at 160 ° C. for 5 hours while stirring in a nitrogen stream. The hydroxyl group equivalent with respect to the solid content of the resin obtained by titration of the solution was 161 g / mol.
Thereafter, 7.39 g (0.034 mol) of di-tert-butyl dicarbonate was added dropwise. Thereafter, 2.68 g (0.034 mol) of pyridine was added dropwise and reacted at room temperature for 3 hours. Thereafter, by reacting at 110 ° C. for 1 hour, the desired resin solution (A) in which 40% of hydrogen in all hydroxyl groups in the resin component contained in the resin solution (A-2) is substituted with a tert-butoxycarbonyl group. -3) was obtained.
20 g of the obtained resin solution (A-3) and 0.37 g of N-hydroxynaphthalimide trifluoromethanesulfonate were mixed to obtain a uniform photosensitive resin composition (A-4).

The obtained photosensitive resin composition (A-4) was applied onto a silicon wafer with a spin coater and dried on a hot plate at 90 ° C. for 3 minutes to form a resin layer having a thickness of 3 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. Then, after heating at 110 ° C. for 5 minutes, heating is performed, and the resin layer is immersed and developed in a 1.0% tetramethylammonium hydroxide aqueous solution for 30 seconds, so that the resin layer in the exposed portion is dissolved and good positive patterning is achieved. The obtained resin layer could be obtained. Then, heat curing was performed at 250 degreeC under nitrogen stream for 1 hour using the hot-air circulation type dryer.

About the obtained resin layer, the following characteristics were measured.
Transmittance: As a measure of transparency, a glass substrate was used instead of a silicon wafer, and coating, drying, exposure, and post-exposure heating were performed in the same manner, followed by heat curing. The light transmittance at a wavelength of 400 nm was measured using a spectrophotometer (UV-160 type, manufactured by Shimadzu Corporation) (unit:%). The higher the transmittance, the better the transparency.
Water absorption: The resin layer peeled from the glass substrate with a resin layer used in the transmittance evaluation 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.
5% thermal weight loss temperature: Using a differential thermal balance (TG / DTA 6200 type, manufactured by Seiko Instruments Inc.), a 5% weight loss temperature was measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere ( Unit, ° C).
The measurement results are shown in Table 1. From Table 1, the obtained resin layer showed a good value in all items.

Example 2
1- (Benzocyclobuten-4-yl) -acrylic acid 9.4 g (0.05 mol), 1-hydroxy-1 was added to a 200 ml four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device. , 2,3-benzotriazole (7.3 g, 0.05 mol) and N-methyl-2-pyrrolidone (59 g) were introduced, stirred and dissolved in a nitrogen stream. Thereafter, the mixture was cooled to 5 to 10 ° C., 14.5 g (0.07 mol) of N, N′-dicyclohexylcarbodiimide was added dropwise together with 10 g of N-methyl-2-pyrrolidone, and the mixture was stirred at room temperature for 15 hours. By-products precipitated in the reaction system were removed with a glass filter, the filtrate was dropped into 100 ml of water, and the precipitated solid was filtered and collected. Then, after washing with 2-propanol, vacuum drying was performed overnight at room temperature to obtain 1- (benzocyclobuten-4-yl) -acrylic acid active ester (A-5).

  Next, 5.4 g (0.018 mol) of (A-5), hexafluoro-2,2-bis (3-) was added to a 100 ml three-necked flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device. Amino-4-hydroxyphenyl) propane (3.4 g, 0.009 mol) and N-methyl-2-pyrrolidone (26.4 g) were introduced and dissolved by stirring under a nitrogen stream. Thereafter, the mixture was stirred at 75 ° C. for 15 hours, and the resulting reaction system was dropped into a mixed solution of 2-propanol and water, and the precipitated solid was filtered and collected, and then dried in a vacuum dryer. The compound (A-6) shown was obtained.

Next, 7.5 g (0.030 mol) of (A-1) obtained in Example 1 was obtained in a 200 ml-containing four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device. 7.6 g (0.007 mol) of 1,3-bis (2-bicyclo [4.2.0] octa-1,3,5-trien-3-ylethenyl) -1, By introducing 1.1 g (0.003 mol) of 1,3,3-tetramethyldisiloxane and 64.8 g of dipropylene glycol methyl ether acetate, the mixture was heated and reacted at 160 ° C. for 5 hours with stirring in a nitrogen stream. A resin solution (A-7) (resin content: 24.6%) was obtained. The hydroxyl group equivalent to the solid content of the resin obtained by titration of the solution was 225 g / mol.
Thereafter, 3.14 g (0.014 mol) of di-tert-butyl dicarbonate was added dropwise. Thereafter, 1.13 g (0.014 mol) of pyridine was added dropwise and reacted at room temperature for 3 hours. Thereafter, by reacting at 110 ° C. for 1 hour, the target resin solution (A) in which 20% of hydrogen in all hydroxyl groups in the resin solution (A-7) is substituted with tert-butoxycarbonyl groups. -8) was obtained.
20 g of the obtained resin solution (A-8) and 0.59 g of N-hydroxynaphthalimide trifluoromethanesulfonate were mixed to obtain a uniform photosensitive resin composition (A-9).
The other evaluations were the same as in Example 1.

Example 3
In a 200 ml four-necked flask equipped with a thermometer, a condenser tube, a nitrogen inlet tube and a stirrer, 2.67 g (0.02 mol) of aluminum chloride (■) and 3.45 g of 1,2-dihydroxybenzoyl chloride (
0.02 mol) and 55.1 g of ethyl acetate were introduced and stirred under a nitrogen stream. Thereafter, the reaction system was cooled, and 1.98 g (0.019 mol) of benzocyclobutene was slowly added dropwise and stirred for 1 hour. Thereafter, a 10% aqueous hydrochloric acid solution and then a 10% aqueous sodium hydroxide solution were added to the reaction system. After extracting and removing the organic layer, a 10% aqueous hydrochloric acid solution was added dropwise until the pH was 3 or less, and the precipitate obtained by filtration was recrystallized from methanol and dried in vacuo at room temperature to obtain a white crystal formula. The compound (A-10) shown by (16) was obtained.

  Next, 7.5 g (0.030 mol) of (A-1) obtained in Example 1 was obtained in a 200 ml four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device. (A-10) 3.1 g (0.013 mol), 1,3-bis (2-bicyclo [4.2.0] octa-1,3,5-trien-3-ylethenyl) -1, By introducing 1.8 g (0.005 mol) of 1,3,3-tetramethyldisiloxane and 37.2 g of dipropylene glycol methyl ether and heating and reacting at 160 ° C. for 5 hours while stirring in a nitrogen stream, Resin solution (A-11) (resin content: 23.4%) was obtained. The hydroxyl group equivalent to the solid content of the resin obtained by titration of the solution was 146 g / mol.

Thereafter, 11.11 g (0.051 mol) of di-tert-butyl dicarbonate was added dropwise. Thereafter, 4.03 g (0.051 mol) of pyridine was added dropwise and reacted at room temperature for 3 hours. Thereafter, by reacting at 110 ° C. for 1 hour, a target resin solution (A) in which 60% of hydrogen in all hydroxyl groups in the resin solution (A-11) is substituted with a tert-butoxycarbonyl group. -12) was obtained.
20 g of the obtained resin solution (A-12) and 0.47 g of 4-methoxy-α-((((4-methylphenyl) sulfonyl) oxy) imino) -benzeneacetonitrile were mixed to obtain a uniform photosensitive resin composition. (A-13) was obtained.
The other evaluations were the same as in Example 1.

Example 4
25.2 g (0.34 mol) of tert-butanol and 100 g of dimethylsulfoxide were introduced into a 200 ml four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device, and stirred under a nitrogen stream. Thereafter, 50.0 g (0.45 mol) of potassium tert-butoxide was added and dissolved while refluxing. To this reaction system, 19.5 g (0.11 mol) of 4-bromobenzocyclobutene was slowly added dropwise and stirred for 7 hours under reflux conditions. Thereafter, this reaction system was added to 300 ml of water to extract and remove the organic layer, and then a 10% hydrochloric acid aqueous solution was added dropwise until the pH became 3 or less. The oil layer separated from the aqueous layer was recovered, 1 g of anhydrous sodium sulfate was added and the mixture was allowed to stand for 1 day, and the solid content was separated by filtration. The oil layer was distilled to obtain the compound (A-14) represented by the formula (17).

  Next, 10.0 g (0.040 mol) of (A-1) obtained in Example 1 was obtained in a 200 ml-filled four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device. (A-14) 2.0 g (0.017 mol), 1,3-bis (2-bicyclo [4.2.0] octa-1,3,5-trien-3-ylethenyl) -1, By introducing 2.2 g (0.006 mol) of 1,3,3-tetramethyldisiloxane and 56.8 g of dipropylene glycol methyl ether acetate and heating and reacting at 160 ° C. for 5 hours while stirring in a nitrogen stream, A resin solution (A-15) (resin content: 23.6%) was obtained. The hydroxyl group equivalent to the solid content of the resin obtained by titration of the solution was 151 g / mol.

Thereafter, 10.29 g (0.047 mol) of di-tert-butyl dicarbonate was added dropwise. Thereafter, 3.73 g (0.047 mol) of pyridine was added dropwise and reacted at room temperature for 3 hours. Thereafter, by reacting at 110 ° C. for 1 hour, the desired resin solution (A) in which 50% of hydrogen in all hydroxyl groups in the resin solution (A-15) is substituted with tert-butoxycarbonyl groups. -16) was obtained.
20 g of the obtained resin solution (A-16) and 0.47 g of 4-methoxy-α-((((4-methylphenyl) sulfonyl) oxy) imino) -benzeneacetonitrile were mixed to obtain a uniform photosensitive resin composition. (A-17) was obtained. The other evaluations were the same as in Example 1.

Example 5
To the resin solution (A-2) obtained in Example 1, 16.9 ml (0.02 mol) of a 1.0 M hydrochloric acid / diethyl ether solution was added dropwise, and then heated to 40 ° C., and 3,4-dihydro- 3.56 g (0.04 mol) of 2H-pyran was added dropwise while paying attention to heat generation, and reacted at 40 ° C. for 4 hours. Then, it cooled to 10 degrees C or less, 1.71 g (0.02 mol) of triethylamine was dripped, and it stirred for 30 minutes. By filtering the obtained resin solution, the target resin solution (A-) in which 50% of hydrogen in all hydroxyl groups of the resin content contained in the resin solution (A-2) was substituted with tetrahydropyranyl groups. 18) was obtained. The other evaluations were the same as in Example 1.

Comparative Example 1
20 g of the resin solution (A-2) obtained in Example 1 and 0.7 g of the photosensitive material represented by the formula (18) were mixed to obtain a uniform photosensitive resin composition (A-19). The other evaluations were the same as in Example 1.

Comparative Example 2
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 While introducing 1.82 g (0.007 mol), triethylamine 20.2 g (0.2 mol), palladium acetate 0.39 g (0.002 mol) and N, N-dimethylformamide 75 mL, stirring in a nitrogen stream Heated at 90 ° C. for 5 hours. 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 added dropwise, the mixture was cooled to 10 ° C or lower, and the filtrate was filtered from the precipitated white crystals. Separately, it was vacuum-dried at room temperature to obtain 1- (benzocyclobuten-4-yl) -acrylic acid (A-20). Next, (A-20) 7.9 g (0.110 mol) obtained in a 100 ml four-necked 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 14.3 g (0.037 mol) and dipropylene glycol methyl acetate 66 mL of ether was introduced and heated at 160 ° C. for 5 hours with stirring in a nitrogen stream to obtain a resin solution (A-21) (resin content: 23.0%). The carboxyl group equivalent with respect to solid content of the obtained resin was 203 g / mol.
20 g of the obtained resin solution (A-21) and 0.7 g of the photosensitive material represented by the formula (18) were mixed to obtain a uniform photosensitive resin composition (A-22). The other evaluations were the same as in Example 1.

Comparative Example 3
In the reaction of the resin solution in Example 1, 2.0 g (0.008 mol) of (A-1) and 1,3-bis (2-bicyclo [4.2.0] octa-1,3,5- (Trien-3-ylethenyl) -1,1,3,3-tetramethyldisiloxane was changed to 7.22 g (0.018 mol) and dipropylene glycol methyl ether acetate to 27.66 g while stirring in a nitrogen stream. A resin solution (A-23) (resin content: 25.3%) was obtained by heating at 160 ° C. for 5 hours. The hydroxyl group equivalent to the solid content of the resin obtained by titration of the solution was 582 g / mol.
Thereafter, 1.38 g (0.006 mol) of di-tert-butyl dicarbonate was added dropwise. Thereafter, 0.50 g (0.006 mol) of pyridine was added dropwise and reacted at room temperature for 3 hours. Thereafter, by reacting at 110 ° C. for 1 hour, the target resin solution (A) in which 40% of hydrogen in all hydroxyl groups in the resin solution (A-23) is substituted with tert-butoxycarbonyl groups. -24) was obtained.
20 g of the obtained resin solution (A-24) and 0.40 g of N-hydroxynaphthalimide trifluoromethanesulfonate were mixed to obtain a uniform photosensitive resin composition (A-25). The other evaluations were the same as in Example 1.

Comparative Example 4
20 g of the resin solution (A-2) obtained in Example 1 and 0.37 g of N-hydroxynaphthalimide trifluoromethanesulfonate were mixed to obtain a uniform photosensitive resin composition (A-26).
The other evaluations were the same as in Example 1.

Comparative Example 5
To the resin solution (A-11) obtained in Example 3, 16.67 g (0.076 mol) of di-tert-butyl dicarbonate was added dropwise. Thereafter, 6.04 g (0.076 mol) of pyridine was added dropwise and reacted at room temperature for 3 hours. Thereafter, by reacting at 110 ° C. for 1 hour, the target resin solution (A) in which 90% of hydrogen in all hydroxyl groups in the resin component contained in the resin solution (A-11) is substituted with a tert-butoxycarbonyl group. -27) was obtained.
20 g of the obtained resin solution (A-27) and 0.47 g of 4-methoxy-α-((((4-methylphenyl) sulfonyl) oxy) imino) -benzeneacetonitrile were mixed to obtain a uniform photosensitive resin composition. (A-28) was obtained.
The other evaluations were the same as in Example 1.

The present invention provides a photosensitive resin composition that 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 a method for forming a resin layer using the same. To do.
By using the photosensitive resin composition 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 excellent transparency and low dielectric constant. An insulating resin layer having 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 or an interlayer insulating film material, and is industrially useful.

Claims (4)

(A) It is obtained by heating and reacting at least one compound represented by the general formulas (1) to (4) and a compound having two or more benzocyclobutene structures in one molecule at 100 to 200 ° C., It is a resin having a hydroxyl group equivalent of 400 g / mol or less , and further, 5 to 80% of hydrogen in all hydroxyl groups contained in the resin is an alkoxycarbonyl group having 2 to 20 carbon atoms and an alkoxy having 2 to 20 carbon atoms. A resin substituted with a group selected from an alkyl group, an alkyl-substituted silyl group having 1 to 10 carbon atoms, a tetrahydropyranyl group, and a tetrahydrofuranyl group, and (B) a compound that generates an acid by light. A photosensitive resin composition.

(R ₁ and R ₃ are a hydrogen atom or an alkyl group having 6 or less carbon atoms, and R ₂ and R ₄ are an alkyl group or a single bond having 6 or less carbon atoms. R ₅ is a 2 having at least one hydroxyl group. R ₆ is —CH ₂ — or —CO—, m is an integer of 0 to 2, n is an integer of 1 to 3, p is an integer of 0 to 2, and q is 1 to 2. It is an integer of 3.) A step of forming a resin layer of the photosensitive resin composition on a substrate using the photosensitive resin composition according to claim 1, a step of performing pattern exposure, a step of performing post-exposure heating, and a resin by development with an alkaline aqueous solution A method for forming a resin layer, comprising a step of patterning a layer, and a step of heating the resin layer at 100 to 250 ° C. in an inert gas. A silicon wafer with a resin layer, wherein a resin layer of the photosensitive resin composition is formed on a silicon wafer using the photosensitive resin composition according to claim 1. A glass substrate with a resin layer, wherein a resin layer of the photosensitive resin composition is formed on a glass substrate using the photosensitive resin composition according to claim 1.