JP2009080390A - Method for producing positive photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a positive photosensitive resin composition, having high sensitivity and superior storage stability. <P>SOLUTION: The method for producing the positive photosensitive resin composition comprises (A) novolac resin, (B) a polyimide precursor which may contain a hydroxyl group and (C) a quinonediazide compound comprises (I) a step of preparing (a) a solution, obtained by dissolving the novolac resin in an organic solvent and (b) a solution, obtained by dissolving the polyimide precursor in an organic solvent, and (II) a step of mixing the solution (a) and the solution (b). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a positive photosensitive resin composition. More specifically, the present invention relates to a method for producing a positive photosensitive resin composition suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc., wherein a portion exposed to ultraviolet rays is dissolved in an alkaline developer. .

  A heat-resistant resin such as polyimide is used for a surface protective film, an interlayer insulating film, and the like of a semiconductor element such as an LSI because of its excellent heat resistance and electrical insulation. With the miniaturization of semiconductor elements, surface protection films, interlayer insulation films, etc. are required to have a resolution of several μm. In such applications, photosensitive resins such as positive photosensitive polyimide that can be finely processed are used. It has been.

The properties of the polyamic acid, which is a polyimide precursor, change due to the progress of imidization in the system when the solution is allowed to stand at room temperature. Therefore, in order to improve storage stability, a method of esterifying polyamic acid has been proposed (see, for example, Patent Document 1). Moreover, as a positive photosensitive resin composition having high sensitivity and high resolution, a positive photosensitive resin composition containing a novolac resin, a polyimide precursor, and a quinonediazide compound has been proposed (for example, see Patent Documents 2 to 3). ).
Japanese Patent Laid-Open No. 2-181149 JP-A-2005-352004 JP-A-2005-250160

  In the positive photosensitive resin composition, when a polyamic acid ester is used as a polyimide precursor, it is necessary to heat for a long time in a mixed state of the polyamic acid ester and a novolak resin in order to dissolve the polyamic acid ester. There was a problem that the sensitivity of the lowering. Moreover, when using a polyamic acid as a polyimide precursor, there existed a subject that it was inferior in storage stability and the sensitivity change was large. An object of the present invention is to provide a method for producing a positive photosensitive resin composition that solves such problems and has high sensitivity and excellent storage stability.

The present invention is a method for producing a positive photosensitive resin composition comprising (A) a novolak resin, (B) a resin mainly composed of a repeating unit represented by the general formula (1), and (C) a quinonediazide compound. And at least (I) (a) a solution obtained by dissolving the novolak resin in an organic solvent, and (b) a resin containing the repeating unit represented by the general formula (1) as a main component in the organic solvent. Preparing a solution comprising:
(II) a step of mixing the solution (a) and the solution (b),
It is a manufacturing method of the positive photosensitive resin composition which has this.

(In the general formula (1), R ¹ represents a trivalent to octavalent organic group having 2 or more carbon atoms, and R ² represents a divalent to octavalent organic group having 2 or more carbon atoms. R ³ and R ⁴ represent Each may be the same or different and represents hydrogen or an organic group having 1 to 20 carbon atoms, provided that 50 mol% or more of each of R ³ and R ⁴ is an organic group having 1 to 20 carbon atoms. Or 2, l represents an integer of 0 to 2. p and q represent an integer of 0 to 4, provided that p + q> 0.

  According to the present invention, a positive photosensitive resin composition having high sensitivity and excellent storage stability can be obtained.

  The positive photosensitive resin composition in the present invention contains (A) a novolak resin, (B) a resin mainly composed of a repeating unit represented by the general formula (1), and (C) a quinonediazide compound.

  First, (A) novolac resin will be described. The type of novolac resin is not particularly limited, and any type may be used as long as it can be generally used for electronic materials. The weight average molecular weight of the novolak resin is preferably 1,000 to 20,000, particularly preferably 2,000 to 10,000, but not limited thereto, from the viewpoint of solubility in an alkali developer. . In addition, the weight average molecular weight in this invention says the value computed using GPC (gel permeation chromatography) measurement by polystyrene conversion.

  Next, (B) the resin mainly composed of the repeating unit represented by the general formula (1) will be described. The resin containing the repeating unit represented by the general formula (1) as a main component can be a resin having an imide ring or other cyclic structure by heating or an appropriate catalyst. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved. Preferably, a polyamic acid ester of a polyimide precursor is used. Here, the main component means that the repeating unit represented by the general formula (1) has 50 mol% or more in the repeating unit of the resin. Preferably it is 70 mol% or more, more preferably 90 mol% or more.

In the general formula (1), R ¹ represents a trivalent to octavalent organic group having 2 or more carbon atoms and represents an acid structural component. The acid R ¹ is trivalent, as the acid, trimellitic acid, tricarboxylic acids such as trimesic acid, R ¹ is tetravalent, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic Mention may be made of tetracarboxylic acids such as acids. Moreover, the acid which has hydroxyl groups, such as a hydroxyphthalic acid and a hydroxy trimellitic acid, can also be mentioned. These acid components may be used alone or in combination of two or more, but preferably contain 1 to 40 mol% of tetracarboxylic acid.

R ¹ preferably contains an aromatic ring from the viewpoint of heat resistance, and more preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms. Specifically, it is preferable that R ¹ (COOR ³ ) _m (OH) _p in the general formula (1) has a structure shown below.

In the general formula (1), R ² represents a divalent to octavalent organic group having 2 or more carbon atoms and represents a structural component of diamine. Of these, those having an aromatic ring are preferred from the viewpoint of the heat resistance of the resulting polymer. Specific examples of the diamine include bis (amino-hydroxy-phenyl) hexafluoropropane having a fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol having no fluorine atom. , Dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, and the like, and R ² (COOR ⁴ ) _l (OH) _{q in} the general formula (1) can have the structures shown below.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure in R ¹ and / or R ² of the general formula (1) may be used as long as the heat resistance is not lowered. Specific examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

R ³ and R ^{4 in} the general formula (1) may be the same or different, and represent hydrogen or an organic group having 1 to 20 carbon atoms. From the viewpoint of storage stability of the resulting photosensitive resin composition, R ³ and R ⁴ are preferably organic groups, but hydrogen is preferable from the viewpoint of solubility in an alkali developer. In the present invention, hydrogen atoms and organic groups can be mixed. By adjusting the amounts of hydrogen and organic groups of R ³ and R ^4, the dissolution rate with respect to the aqueous alkali solution is changed, so that a photosensitive resin composition having an appropriate dissolution rate can be obtained by this adjustment. As for the range in this invention, 50 mol% or more of each of R < ³ >, R < ⁴ > is a C1-C20 organic group. If 50 mol% or more of each of R ³ and R ⁴ is an organic group having 1 to 20 carbon atoms, it is possible to obtain a photosensitive resin composition having excellent storage stability and an appropriate dissolution rate in an aqueous alkali solution. it can. When the number of carbon atoms in R ³ and R ⁴ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the above, R ³ and R ⁴ are each required to be a hydrocarbon group having 1 to 20 carbon atoms in an amount of 50 mol% or more.

  (B) In the resin whose main component is the repeating unit represented by the general formula (1), the number of the repeating units represented by the general formula (1) is preferably in the range of 10 to 100,000. In view of solubility of the polymer in an alkali developer, the number of repeating units is more preferably 1,000 or less, and even more preferably 100 or less. Further, the number of repeating units is more preferably 20 or more from the viewpoint of improving the elongation. The number of repeating units is Mw / M, where M is the molecular weight of the repeating unit and Mw is the weight average molecular weight of the polymer. The number of repeating units in the present invention refers to a value calculated using GPC measurement in terms of polystyrene.

  (B) The resin mainly composed of the repeating unit represented by the general formula (1) is synthesized by the following method. For example, a method of reacting in the presence of a diamine compound, a monoamino compound and a condensing agent after obtaining a diester with a tetracarboxylic dianhydride and an alcohol, a diester being obtained with a tetracarboxylic dianhydride and an alcohol, and the remaining A method of acidifying dicarboxylic acid and reacting with diamine compound, monoamino compound, after reacting tetracarboxylic dianhydride and diamine compound, monoamino compound used for terminal blocking at low temperature, glycidyl compound, acetal compound, etc. There is a method of esterifying a carboxylic acid with an esterifying agent.

  In the polymerization liquid after polymerizing the resin mainly composed of the repeating unit represented by the general formula (1) by the above method, unreacted monomers, oligomer components such as dimers and trimers, In addition, impurities generated by esterification such as chlorides or esterification agents accompanying acid chloride conversion of a condensing agent or dicarboxylic acid are contained. Therefore, in order to improve the purity of the resin, it is more preferable to put it in a large amount of water or an organic solvent such as methanol, precipitate it, filter it, dry it and isolate it. In this case, the resulting resin is in a solid state and needs to be dissolved in an organic solvent in order to obtain a positive photosensitive resin composition.

  (B) The content of the resin whose main component is the repeating unit represented by the general formula (1) is preferably 30 parts by weight or more, more preferably 40 parts by weight or more with respect to 100 parts by weight of the (A) novolak resin. . If it is this range, the mechanical characteristic after thermosetting will improve more. Moreover, in order to improve a sensitivity more, 100 weight part or less is preferable and 80 weight part or less is more preferable.

  Next, (C) a quinonediazide compound will be described. The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, a sulfonic acid of quinonediazide in an ester bond and / or sulfone Examples include amide-bonded ones. From the viewpoint of the contrast between the exposed area and the unexposed area, it is preferable that 50 mol% or more of the entire functional group is substituted with quinonediazide. By using such a quinonediazide compound, it is possible to obtain a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp that is a general ultraviolet ray. it can.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. Further, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used together.

  In addition, the molecular weight of the quinonediazide compound is preferably 1500 or less, and more preferably 1200 or less. When the molecular weight is 1500 or less, the quinonediazide compound is sufficiently thermally decomposed in the heat treatment after pattern formation, and a cured film having excellent heat resistance, mechanical properties, and adhesiveness can be obtained. On the other hand, 300 or more is preferable and 350 or more is more preferable.

  The content of the (C) quinonediazide compound is preferably 1 part by weight or more, more preferably 3 parts by weight or more, with respect to 100 parts by weight of the total amount of the (A) novolak resin and the resin of the component (B). , Preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  In the present invention, the positive photosensitive resin composition may contain a compound containing an alkoxymethyl group in order to obtain excellent mechanical properties when heated and cured. Moreover, you may contain a silane compound in order to improve adhesiveness with a base substrate. You may contain the compound containing a phenolic hydroxyl group for the purpose of improving a sensitivity. Surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane for the purpose of improving the coatability with the base substrate May also be included. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  In the present invention, the positive photosensitive resin composition may contain an organic solvent. Organic solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether Ethers such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetone alcohol, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, and aromatic hydrocarbons such as toluene and xylene .

  In the present invention, these solvents can be used alone or in combination of two or more. The content of the solvent is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and preferably 2000 parts by weight with respect to 100 parts by weight of the total amount of the polymer of (a) novolak resin and component (b). Part or less, more preferably 1500 parts by weight or less.

  The manufacturing method of the positive photosensitive resin composition of this invention is demonstrated. First, (I) (a) a solution obtained by dissolving the novolak resin in an organic solvent, and (b) a resin containing a repeating unit represented by the general formula (1) as a main component in an organic solvent. The process for preparing the solution will be described. In any of the solutions, the organic solvents listed above can be used.

  A novolac resin is dissolved in an organic solvent, and (a) a solution prepared by dissolving the novolac resin in the organic solvent is prepared. A solution obtained by dissolving a mixed solution of a novolak resin and an organic solvent at 30 to 60 ° C. is preferable. If the temperature at the time of melting is 30 ° C. or higher, the time required for the melting step is shortened. Moreover, in order to improve initial sensitivity more, 60 degrees C or less is preferable.

  A resin mainly composed of the repeating unit represented by the general formula (1) is dissolved in an organic solvent, and (b) a resin mainly composed of the repeating unit represented by the general formula (1) is dissolved in the organic solvent. Prepare a solution. As described above, the resin of component (B) is preferably re-precipitated. Since the resin obtained here is in a solid state, it must be dissolved in an organic solvent. A solution obtained by dissolving a mixed solution of a resin mainly composed of the repeating unit represented by the general formula (1) and an organic solvent at 30 to 60 ° C. is preferable. If it is 30 degreeC or more, time required for a melt | dissolution process will become short. Moreover, in order to improve initial sensitivity more, 60 degrees C or less is preferable and 50 degrees C or less is more preferable.

  In the step (I), from the viewpoint of production efficiency, the dissolution time is preferably 20 hours or less, and more preferably 10 hours or less.

  Next, (II) the step of mixing the solution (a) and the solution (b) will be described. In order to further improve the initial sensitivity of the obtained positive photosensitive resin composition, the liquid temperature at the time of mixing the (a) solution and the (b) solution is preferably 40 ° C. or lower. More preferably, it is 10 degreeC or more and 30 degrees C or less. In order to further improve the initial sensitivity, the time for the mixing step is preferably within 2 hours, more preferably within 1 hour.

  A feature of the present invention is that (A) a novolak resin and (B) a resin mainly composed of a repeating unit represented by the general formula (1) are dissolved separately. As described above, the resin of component (B) is generally re-precipitated and used as a solid resin. When such a solid resin and a novolak resin are used in combination, it is necessary to heat them under the coexistence conditions of the component (A) and the component (B) in order to dissolve them together in an organic solvent. The positive photosensitive resin composition obtained by such a method could not obtain sufficient sensitivity. The reason is not clear, but it is considered that one reason is that the novolak resin deteriorates due to the influence of oxidation or the like by heating under the coexistence conditions of both resins. Therefore, in the present invention, by mixing each resin separately, the mixing step of (A) a novolac resin and (B) a resin mainly composed of a repeating unit represented by the general formula (1) is performed at a low temperature and Since it can be done in a short time, it is not necessary to heat in a mixed state for a long time, and a highly sensitive positive photosensitive resin composition can be obtained.

  (C) The order in which the quinonediazide compound and, if necessary, other components are dissolved in an organic solvent is not particularly limited. You may add to (a) solution or (b) solution, and may add after mixing (a) solution and (b) solution.

  Examples of the dissolution method in each step include a method of stirring and dissolving with a mechanical stirrer in a glass flask or stainless steel container, a method of dissolving with ultrasonic waves, a method of stirring and dissolving with a planetary stirring and deaerator, and the like. .

  In each step, filtration may be performed with a filter having a pore size of 0.1 μm to 5 μm in order to remove foreign substances.

  Next, a method for forming a heat-resistant resin pattern using the positive photosensitive resin composition of the present invention will be described.

  A positive photosensitive resin composition is applied on the substrate. Examples of the substrate include, but are not limited to, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, and ITO. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

  Next, the substrate coated with the positive photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.

  Next, the photosensitive resin film is exposed to actinic radiation through a mask having a desired pattern. Examples of actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. In the present invention, i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp are used. preferable.

  In order to form a pattern of a heat resistant resin from the photosensitive resin film, the exposed portion may be removed using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Add alcohols such as isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of several kinds. Also good. After development, it is preferable to rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 200 ° C. to 500 ° C. is applied to convert it to a heat resistant resin film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and increasing the temperature stepwise or by selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 320 ° C. over 2 hours can be mentioned.

  The heat-resistant resin film formed by the positive photosensitive resin composition of the present invention includes a semiconductor passivation film, a surface protection film of a semiconductor element, an interlayer insulating film of a multilayer wiring for high-density mounting, an insulating layer of an organic electroluminescent element, etc. It is suitably used for applications.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the positive photosensitive resin composition in an Example was performed with the following method.

(1) Solubility Evaluation In the dissolution step when producing a positive photosensitive resin composition (hereinafter referred to as varnish), the time until the novolak resin and the polyimide precursor were dissolved was visually evaluated. The time for the resin to dissolve is better, and if the time until each resin dissolves is within 10 hours, ○, if any is 10 hours or more and less than 20 hours, Δ is either 20 hours When it was not dissolved, it was marked as x.

(2) Evaluation of pattern processability Production of photosensitive resin film On a 6-inch silicon wafer, varnish was applied so that the film thickness after pre-baking was T1 = 8.5 μm, and then hot plate (manufactured by Tokyo Electron Ltd.) A photosensitive resin film was obtained by pre-baking at 120 ° C. for 3 minutes using a coating and developing apparatus Mark-7).

Measurement of film thickness Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film thickness after pre-baking and after development was measured at a refractive index of 1.629.

Exposure exposure machine (GCA Corp. i-line stepper DSW-8570i), sets the reticle cut the pattern, at the exposure wavelength of i-line (365 nm), the range the exposure amount of 100mJ ^/ cm ² ~800mJ ^/ cm 2 The photosensitive resin film was exposed by changing in steps of 20 mJ / cm ² .

Development A 2.38 wt% aqueous solution of tetramethylammonium hydroxide was sprayed on the exposed film for 10 seconds at 50 revolutions using a Mark-7 developing device manufactured by Tokyo Electron Ltd. Then, it was allowed to stand for 30 seconds at 0 rotation, rinsed with water at 400 rotation, and shaken and dried for 10 seconds at 3000 rotation.

Calculation of Sensitivity After exposure and development, the minimum exposure time (hereinafter referred to as the optimum exposure time) Eop1 at which a 50 μm line and space pattern (1L / 1S) is formed in a one-to-one width was determined. When the value of Eop1 was 300 mJ / cm ² or less, it was good, and when it exceeded 300 mJ / cm ² , it was regarded as defective.

(3) Storage stability evaluation After leaving the varnish for 14 days at 23 ° C. under a yellow light, a prebaked film having a film thickness T1 = 8.5 μm was prepared, exposed and developed in the same manner as the above evaluation, and the optimal exposure time. Eop2 was determined. A value of Eop2-Eop1 was calculated, and if the absolute value of this value was 50 mJ / cm ² or less, it was judged good, and if it exceeded 50 mJ / cm ² , it was judged as bad.

Synthesis Example 1 Synthesis of hydroxyl group-containing diamine 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was added to 100 mL of acetone and 17.4 g of propylene oxide (0 3 mol) and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine represented by the following formula.

Synthesis Example 2 Synthesis of Novolak Resin Under a dry nitrogen stream, 108.0 g (1.00 mol) of m-cresol, 75.5 g of 37 wt% formaldehyde aqueous solution (0.93 mol of formaldehyde), 0.63 g of oxalic acid dihydrate (0.005 mol) and 264 g of methyl isobutyl ketone were charged, followed by immersion in an oil bath, and a polycondensation reaction was performed for 4 hours while the reaction solution was refluxed. Thereafter, the temperature of the oil bath is raised over 3 hours, and then the pressure in the flask is reduced to 4.0 kPa to 6.7 kPa to remove volatile components, and the dissolved resin is cooled to room temperature. Thus, a polymer solid of novolak resin was obtained. From GPC, the weight average molecular weight was 3,500.

Synthesis Example 3 Synthesis of Polymer A Under a dry nitrogen stream, 24.17 g (0.040 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 1,3-bis (3-aminopropyl) tetramethyldisiloxane ( 1.24 g (0.005 mol) of SiDA was dissolved in 50 g of NMP. To this, 15.51 g (0.05 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic anhydride (ODPA) was added together with 21 g of NMP and reacted at 20 ° C. for 1 hour, and then at 50 ° C. for 1 hour. Reacted. Thereafter, 1.17 g (0.010 mol) of 4-ethynylaniline was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 1 hour. Thereafter, a solution obtained by diluting 13.2 g (0.090 mol) of N, N-dimethylformamide diethyl acetal with 15 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried in a vacuum dryer at 80 ° C. for 72 hours to obtain a polyimide precursor polymer A. As a result of calculating the number of repeating units from GPC, the number of repeating units of Polymer A was 35.

Synthesis Example 4 Synthesis of Polymer B In a dry nitrogen stream, 48.1 g of 4,4′-diaminophenyl ether and 25.6 g of SiDA were dissolved in 820 g of NMP, and 105 g of ODPA was added, while adjusting the temperature to be 10 ° C. or higher and 30 ° C. or lower. By stirring for a time, a polymer solution B of polyimide precursor was obtained.

Examples 1-23
7 g of the novolak resin obtained in Synthesis Example 2 was added to 15 g of GBL, the temperature was adjusted to the melting temperature of the novolak resin described in Table 1, and stirring was performed for the time shown in Table 1 as the dissolution time of the novolak resin while visually confirming the dissolution. (A) A liquid was obtained. Next, 4 g of the polymer A4g obtained in Synthesis Example 3 and 2.2 g of MG-300 (trade name, manufactured by Toyo Gosei Co., Ltd.) as the quinonediazide compound were added to 15 g of GBL, and the polyimide precursor dissolution temperature described in Table 1 was added. The solution was stirred for the time shown in Table 1 as the dissolution time of the polyimide precursor while visually confirming dissolution, to obtain a liquid (b). The resin solubility was evaluated from the dissolution time of each resin at this time.

  Furthermore, the liquid (a) and the liquid (b) are respectively adjusted to the temperature of the liquid mixture (a) liquid + (b) described in Table 1, the liquid (a) and the liquid (b) are mixed and stirred, and the varnish Got. The mixing time of liquid (a) and liquid (b) was set to (a) liquid + (b) liquid mixing time described in Table 1. Using the obtained varnish, pattern processability evaluation and storage stability evaluation were performed as described above. The evaluation results are shown in Table 1.

Comparative Examples 1-3
7 g of the novolak resin obtained in Synthesis Example 2 was added to 30 g of GBL, and the temperature was adjusted to 40 ° C. and stirred, and dissolved for the time shown in Table 2 as the dissolution time of the novolak resin while visually confirming dissolution. Next, the temperature of the reaction solution was adjusted to the polyimide precursor dissolution temperature described in Table 2, and the polymer A4g obtained in Synthesis Example 3 and MG-300 (trade name, manufactured by Toyo Gosei Co., Ltd.) 2.2 g as the quinonediazide compound. Was added and stirred for the time shown in Table 2 as dissolution time of the polyimide precursor while visually confirming dissolution to obtain a varnish. The resin solubility was evaluated from the resin dissolution time at this time. Using the obtained varnish, pattern processability evaluation and storage stability evaluation were performed as described above. The evaluation results are shown in Table 2.

Comparative Example 4
Into 30 g of GBL, 7 g of the novolak resin obtained in Synthesis Example 2, 4 g of the polymer A obtained in Synthesis Example 3, and 2.2 g of MG-300 (trade name, manufactured by Toyo Gosei Co., Ltd.) as a quinonediazide compound were added. The mixture was stirred at 5 ° C. while visually confirming dissolution to obtain a varnish. At this time, the dissolution time of the resin was 5 hours, and the solubility was evaluated as ◯. Table 3 shows the results of pattern workability evaluation and storage stability evaluation as described above using the obtained varnish.

Comparative Example 5
7 g of the novolak resin obtained in Synthesis Example 2 and 2.2 g of MG-300 (trade name, manufactured by Toyo Gosei Co., Ltd.) as the quinonediazide compound were added to 15 g of GBL, and the temperature was adjusted to 40 ° C. and dissolved visually. The mixture was stirred for 4 hours while confirming the above to obtain a liquid (a). At this time, the dissolution time of the resin was 4 hours, and the solubility was evaluated as ◯. Next, 20 g of the polymer B solution obtained in Synthesis Example 4 and the liquid (a) were temperature-controlled at 25 ° C., and the polymer B solution and the liquid (a) were mixed and stirred for 30 minutes to obtain a varnish. Table 3 shows the results of pattern workability evaluation and storage stability evaluation as described above using the obtained varnish.

Claims (3)

(A) a novolak resin, (B) a resin having a repeating unit represented by the general formula (1) as a main component, and (C) a positive photosensitive resin composition containing a quinonediazide compound, (I) (a) a solution obtained by dissolving the novolak resin in an organic solvent, and (b) a solution obtained by dissolving a resin containing the repeating unit represented by the general formula (1) as a main component in an organic solvent. Preparing the process,
(II) a step of mixing the solution (a) and the solution (b),
The manufacturing method of the positive photosensitive resin composition which has this.

(In the general formula (1), R ¹ represents a trivalent to octavalent organic group having 2 or more carbon atoms, and R ² represents a divalent to octavalent organic group having 2 or more carbon atoms. R ³ and R ⁴ May be the same or different and each represents hydrogen or an organic group having 1 to 20 carbon atoms, provided that 50 mol% or more of each of R ³ and R ⁴ is an organic group having 1 to 20 carbon atoms. 1 or 2, l represents an integer of 0 to 2. p and q represent an integer of 0 to 4, provided that p + q> 0. The solution obtained by dissolving (a) novolak resin in an organic solvent is a solution obtained by dissolving a mixed solution of novolak resin and organic solvent at 30 to 60 ° C., and (b) the general formula A solution obtained by dissolving a resin having a repeating unit represented by (1) as a main component in an organic solvent is a mixture of a resin having a repeating unit represented by general formula (1) as a main component and an organic solvent. The method for producing a positive photosensitive resin composition according to claim 1, wherein the solution is a solution obtained by dissolving at 30 to 60 ° C. The positive type according to claim 2, wherein the liquid temperatures of the (a) solution and the (b) solution in the step of mixing the (II) (a) solution and the (b) solution are both 40 ° C. or less. A method for producing a photosensitive resin composition.