JP2014137434A - Positive photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photosensitive resin composition having excellent adhesiveness to copper and a copper alloy.SOLUTION: The positive photosensitive resin composition comprises (a) a resin described below, (b) a quinonediazide compound, (c) a thermal crosslinking agent, and (d) a solvent. In (a) the resin, the sum of numbers of structural units expressed by general formula (1) and by general formula (2) is 50% or more of the number of the whole structural units; and p/(p+q), where p is the number of structural units expressed by general formula (1) and q is the number of structural units expressed by general formula (2), ranges from 0.60 to 0.95.

Description

  The present invention relates to a positive photosensitive resin composition. More specifically, a positive photosensitive resin composition suitably used for an electrode made of copper and a copper alloy, an insulating film in contact with a wiring, for example, a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc. About.

  Conventionally, polyimide-based resins, polybenzoxazole-based resins, and polyamide-imide-based resins that are excellent in heat resistance, mechanical properties, and the like have been widely used for surface protection films and interlayer insulating films of semiconductor elements. Conventionally, after first forming a coating film in the state of a heat-resistant resin precursor having high solubility in an organic solvent, patterning is performed using a photoresist based on a novolak resin and the precursor is heated and cured. Thus, a method of making an insoluble and infusible heat resistant resin has been taken. In recent years, the photoresist process has been simplified by using negative and positive photosensitive resin compositions that can themselves be patterned.

  In addition, in order to reduce the size, integration, and speed of semiconductor elements, miniaturization of metal wiring and multilayer wiring are being promoted. By miniaturization, the gate delay inside the transistor is reduced and contributes to speeding up. On the other hand, in the wiring, the wiring resistance and the capacitance between the wirings increase to cause signal delay. As miniaturization progresses, the decrease in operation speed due to this signal delay has become a level that cannot be ignored.In recent years, the replacement of wiring materials from aluminum, which has been used for general purposes, to copper and copper alloys with low specific resistance has been carried out. It is being advanced.

  When the surface protective film and the interlayer insulating film are formed directly on the wiring, the adhesion between them and the wiring greatly affects the reliability of the semiconductor element. At present, copper and copper alloys have been widely used as wiring materials, and there is a need for a photosensitive resin composition that can form a cured film that is in close contact with these metals.

  In response to such demands, a method of adding a low-molecular additive component to a resin composition in order to improve adhesion to copper and a copper alloy (see, for example, Patent Documents 1 to 3), a specific polybenzoxazole A photosensitive resin composition including a polyamide resin having a precursor structure and having at least one nitrogen-containing cyclic compound at a side chain and a terminal and a photosensitive agent (see Patent Document 4) is known. However, although these methods improve the adhesion with copper and copper alloy immediately after the formation of the cured film, the adhesion strength decreases with the influence of moisture in the air over time. On the other hand, increasing the amount of low molecular additives and introduction of nitrogen-containing cyclic compounds into the resin ends / side chains to maintain adhesion strength leads to a decrease in the mechanical properties, heat resistance, and chemical resistance of the cured film, thereby protecting the surface. There was a problem that it was not suitable for use as a film / interlayer insulating film.

Japanese Patent Laying-Open No. 2005-336125 (page 1-3) Japanese Patent Laying-Open No. 2005-173528 (page 1-2) JP 2006-184660 A (pages 1-7) JP 2009-75546 A (page 1-3)

  An object of the present invention is to provide a positive photosensitive resin composition that is excellent in adhesion with copper and a copper alloy and that can provide a cured film with a small decrease in adhesion strength even when exposed to heated and humidified conditions. To do.

  In order to solve the above problems, the positive photosensitive resin composition of the present invention has the following constitution. That is, (a) the sum of the number of structural units represented by general formula (1) and the number of structural units represented by general formula (2) is 50% or more of the total number of structural units, and the general formula (1) P / (p + q) = 0.60 to 0.95, (b) a quinonediazide compound, wherein p is the number of structural units represented by q and q is the number of structural units represented by the general formula (2), c) A positive photosensitive resin composition comprising a thermal crosslinking agent and (d) a solvent.

(In General Formulas (1) and (2), X is a divalent to tetravalent organic group having 3 to 40 carbon atoms, and the group represented by X— (R ¹ ) _m is the following (Z-1): What is not included in the group, Y is a divalent to hexavalent organic group having 4 to 40 carbon atoms, Z is one or more groups selected from the following group (Z-1): R ¹ is the same or different. at best, .R ² showing a hydroxyl group or ^{O-R 3} may be the same or different, a hydroxyl group, a carboxyl group, .R ³ showing the ^{O-R 3} or ^{COO-R 3} is 1 to 15 carbon atoms An organic group, and either R ¹ or R ² contains a hydroxyl group or a carboxyl group, m is an integer of 0-2, n is an integer of 0-4, and m + n> 1.

(R ⁴ represents a hydrogen atom, a hydroxyl group, a mercapto group, or a monovalent hydrocarbon group having 1 to 10 carbon atoms.)

  The positive photosensitive resin composition of the present invention is excellent in adhesiveness with copper and copper alloys, and can provide a cured film having a small decrease in adhesive strength even when exposed to warming and humidifying conditions.

In the positive photosensitive resin composition of the present invention, (a) the total number of structural units represented by general formula (1) and the number of structural units represented by general formula (2) is 50% of the total number of structural units. In the above, p / (p + q) = 0.60-0.95, where p is the number of structural units represented by general formula (1) and q is the number of structural units represented by general formula (2). It contains a certain resin, (b) a quinonediazide compound, (c) a thermal crosslinking agent, and (d) a solvent. In the general formula (1), the group represented by X— (R ¹ ) _m is not included in the (Z-1) group, and the structure and the general formula represented by the general formula (1) The structure represented by (2) is different.

  In the present invention, the triazine ring or pyrimidine ring contained in the resin of component (a) strongly interacts with copper and a copper alloy, and a cured film having excellent adhesion can be obtained. Since these are introduced into the resin as a part of the main chain structure, each resin molecule has a plurality of sites that interact with copper and a copper alloy, and high adhesion strength can be obtained. Further, unlike low molecular additives, the mechanical properties, heat resistance, and chemical resistance of the cured film are not impaired.

  The resin of component (a) used in the present invention is, for example, a compound selected from a diamine having a structure of X, bis (aminophenol), 2,4-diaminophenol, etc., 1,3 having a structure of Z A compound selected from a 5-triazine-2,4-diamine derivative, a pyrimidine-2,4-diamine derivative, or a pyrimidine-2,6-diamine derivative, and a tetracarboxylic acid, tricarboxylic acid, dicarboxylic acid having the structure of Y or It is obtained by reacting a compound selected from derivatives of these acid anhydrides, acid chlorides, active esters and the like.

In the general formula (1), R ¹ may be the same or different, and represents a hydroxyl group or O—R ³ . In the general formulas (1) and (2), R ² may be the same or different and represents a hydroxyl group, a carboxyl group, O—R ³ or COO—R ³ . Further, either R ¹ or R ² contains a hydroxyl group or a carboxyl group. m is an integer of 0 to 2, n is an integer of 0 to 4, and m + n> 1.

In the general formula (1) and ^{(2), O-R 3} , COO-R 3 as a substituent of ^O-R 3, Y as a substituent of X is a hydroxyl in order to adjust the solubility in an alkali aqueous solution Or it is the group which protected the carboxyl group with the C1-C15 organic group. Examples of R ³ include formyl group, methyl group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. It is done.

  When this polyamide resin is heated at about 200 to 400 ° C., it undergoes dehydration and ring closure, and a heat-resistant resin comprising polyimide, polybenzoxazole, or a copolymer of both is obtained.

  Examples of X in the general formula (1) include, but are not limited to, the following structures, and two or more of these may be used.

Wherein W is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, R ⁵ represents one group or atom selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different, and r is an integer of 0 to 4. R ⁶ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom.)
Among these, particularly preferable structures include structures of the following group (X-1), and two or more of these may be used.

(R ⁵ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different. R is an integer of 0 to 4.)
Among these, a more preferable structure is the structure of the following (X-2) group, and it is more preferable that 20 to 100% of X is a group selected from the (X-2) group. By doing so, a highly sensitive positive photosensitive resin composition can be obtained without impairing chemical resistance.

  Examples of Y in general formulas (1) and (2) include, but are not limited to, the following structures, and two or more of these may be used.

Wherein W is —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, R ⁷ represents one group or atom selected from an alkyl group and a halogen atom, which may be the same or different, and s is an integer of 0 to 2.)
Among these, particularly preferred structures include the following (Y-1) group structures, and two or more of these may be used.

R ⁷ represents one selected from an alkyl group and a halogen atom, and may be the same or different. s is an integer of 0-2.

Z in the general formula (2) represents one or more groups selected from the group (Z-1). R ⁴ represents a hydrogen atom, a hydroxyl group, a mercapto group, or a hydrocarbon group having 1 to 10 carbon atoms. Examples of diamines corresponding to Z include 2,4-diamino-1,3,5-triazine (guanamine), 2,4-diamino-6-methyl-1,3,5-triazine (acetoguanamine), 2,4-diamino-6-phenyl-1,3,5-triazine (benzoguanamine), 2,4-diamino-6-vinyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1 , 3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, 2,4-diaminopyrimidine, 2,4-diamino-6-methylpyrimidine, 2,4-diamino-6 -Phenylpyrimidine, 2,4-diamino-6-vinylpyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,6-diamidine Pyrimidine, 4,6-diamino-2-methylpyrimidine, 4,6-diamino-2-phenylpyrimidine, 4,6-diamino-2-vinylpyrimidine, 4,6-diamino-2-hydroxypyrimidine, 4,6- Although diamino-2-mercaptopyrimidine is mentioned, it is not limited to these, Moreover, you may use 2 or more types of these.

  In the resin of component (a), p / (p + q) = 0.60, where p is the number of structural units represented by general formula (1) and q is the number of structural units represented by general formula (2). 0.95. By setting it as this range, it is excellent in adhesiveness with copper and a copper alloy, and even if it exposes to heating and humidification conditions, the cured film with a small fall of adhesive strength can be obtained. If it exceeds 0.95, the adhesion to copper and copper alloy is insufficient. Conversely, if it is less than 0.60, it is difficult to increase the molecular weight during polymerization and the solubility in an organic solvent is lowered, which is not preferable.

  Further, in order to improve the storage stability of the positive photosensitive resin composition, the resin of component (a) has a main chain terminal such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound, etc. It is preferable to seal with a terminal sealing agent. The introduction ratio of the monoamine used as the terminal blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, preferably 60 mol% or less, particularly preferably 50, based on the total amine component. It is less than mol%. The introduction ratio of the acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound used as the end-capping agent is preferably 0.1 mol% or more, particularly preferably 5 mol%, relative to the diamine component. Or more, preferably 100 mol% or less, particularly preferably 90 mol% or less. A plurality of different end groups may be introduced by reacting a plurality of end-capping agents.

  For the purpose of improving the chemical resistance of the cured resin film obtained by baking, as these end-capping agents, monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds having at least one alkenyl group or alkynyl group, Mono-active ester compounds can also be used.

  Examples of preferable end-capping agents include, but are not limited to, the following structures, and two or more of these may be used.

  The positive photosensitive resin composition of the present invention contains (b) a quinonediazide compound. By containing the quinonediazide compound, an acid is generated in the ultraviolet-exposed area, and the solubility of the exposed area in an alkaline aqueous solution is increased. Therefore, a positive pattern can be obtained by alkali development after the ultraviolet exposure.

  The component (b) used in the present invention may contain two or more quinonediazide compounds. Thereby, the ratio of the dissolution rate of the exposed part and the unexposed part can be increased, and a highly sensitive positive photosensitive resin composition can be obtained.

  Examples of the component (b) used in the present invention include those in which a sulfonic acid of quinonediazide is ester-bonded to a polyhydroxy compound, a compound in which a sulfonic acid of quinonediazide is bonded to a polyamino compound, and a sulfone of quinonediazide to a polyhydroxypolyamino compound. Examples of the acid include an ester bond and / or a sulfonamide bond. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are 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. .

  In the present invention, the quinonediazide compound is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. A compound having both of these groups in the same molecule may be used, or a compound using different groups may be used in combination.

  The component (b) used in the present invention can be synthesized by a known method. For example, a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a polyhydroxy compound in the presence of triethylamine can be mentioned.

  The content of the component (b) used in the present invention is preferably 3 to 40 parts by weight with respect to 100 parts by weight of the resin of the component (a). By setting the content of the quinonediazide compound within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.

  The positive photosensitive resin composition of the present invention contains (c) a thermal crosslinking agent. As the thermal crosslinking agent in the present invention, a compound having at least two alkoxymethyl groups and / or methylol groups is preferably used. By containing these compounds, a condensation reaction is caused with the resin of component (a) during baking after patterning to form a crosslinked structure, and the mechanical properties of the cured film are improved. Further, two or more kinds of thermal cross-linking agents may be used, which enables a wider range of designs.

  Preferred examples of the component (c) used in the present invention include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML. -PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM -PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM -BPE, TMOM-BPA, TMOM-B AF, TMOM-BPAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKACALAC MX-750LM (the trade name, manufactured by Sanwa Chemical Co., Ltd.). Two or more of these may be contained.

  The content of the component (c) used in the present invention is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, more preferably 10 parts by weight with respect to 100 parts by weight of the resin of the component (a). Above, preferably 300 parts by weight or less, more preferably 200 parts by weight or less.

  The positive photosensitive resin composition of the present invention contains (d) a solvent. Preferred examples of the component (d) include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, and dioxane. , Ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, 3-methyl-3 -Esters such as methoxybutyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene, etc. And aromatic hydrocarbons. Two or more of these may be contained. As for content of (d) component, 100-1500 weight part is preferable with respect to 100 weight part of resin of (a) component.

  The positive photosensitive resin composition of the present invention may contain a thermal acid generator as necessary. By containing a thermal acid generator, a cured film having a high crosslinking rate, benzoxazole ring closure rate, and imide ring closure rate can be obtained even when firing at 200 to 300 ° C., which is lower than usual.

  The positive photosensitive resin composition of the present invention may contain a low molecular compound having a phenolic hydroxyl group as long as it does not reduce the shrinkage residual film ratio after curing. By containing the low molecular weight compound having a phenolic hydroxyl group, it is easy to adjust the alkali solubility during pattern processing.

  The positive photosensitive resin composition of the present invention may contain a resin having a phenolic hydroxyl group such as novolak or polyhydroxystyrene as long as the heat resistance and the chemical resistance are not lowered, if necessary. By containing these resins, the sensitivity can be improved.

  The positive photosensitive resin composition of the present invention is a surfactant, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone for the purpose of improving the wettability with the substrate as necessary. , Ketones such as methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane.

  The positive photosensitive resin composition of the present invention may contain inorganic particles. Preferred specific examples include, but are not limited to, silicon oxide, titanium oxide, barium titanate, alumina, talc and the like. The primary particle diameter of these inorganic particles is preferably 100 nm or less, particularly preferably 60 nm or less.

  It also contains a silane coupling agent such as trimethoxyaminopropyl silane, trimethoxy epoxy silane, trimethoxy vinyl silane, trimethoxy thiol propyl silane as long as storage stability is not impaired in order to enhance adhesion to the silicon substrate. May be. A preferable content is 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin of component (a).

  The viscosity of the positive photosensitive resin composition of the present invention is preferably 2 to 5000 mPa · s. By adjusting the solid content concentration so that the viscosity is 2 mPa · s or more, it becomes easy to obtain a desired film thickness. On the other hand, when the viscosity is 5000 mPa · s or less, it becomes easy to obtain a highly uniform coating film. A resin composition having such a viscosity can be easily obtained by setting the solid content concentration to 5 to 60% by weight, for example.

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

  The positive photosensitive resin composition of the present invention is applied to a substrate. As the substrate, a wafer made of silicon, ceramics, gallium arsenide, or the like on which a metal is formed as an electrode or wiring is used, but is not limited thereto. In particular, the present invention provides a cured film having excellent adhesion to electrodes and wirings made of copper and a copper alloy. Therefore, it is more preferable to use a substrate in which a copper-based metal is formed as electrodes and wirings. Examples of the application method include spin coating using a spinner, spray coating, and roll coating. Moreover, although a coating film thickness changes with application methods, solid content concentration of composition, viscosity, etc., it is normally applied so that the film thickness after drying is 0.1 to 150 μm.

  In order to enhance the adhesion between the substrate such as a silicon wafer and the positive photosensitive resin composition, the substrate can be pretreated with the aforementioned silane coupling agent. For example, a solution in which 0.5 to 20% by weight of a silane coupling agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. Surface treatment is performed by spin coating, dipping, spray coating, steam treatment or the like. In some cases, a heat treatment at 50 to 300 ° C. is then performed to advance the reaction between the substrate and the silane coupling agent.

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

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

  In order to form the pattern of the heat resistant resin, after the exposure, the exposed portion is removed using a developer. Developers include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl 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, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. 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 the development, a temperature of 150 to 500 ° C. is applied to advance a thermal crosslinking reaction, an imide cyclization reaction, and an oxazole cyclization reaction to improve heat resistance and chemical resistance. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned.

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

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited by these examples. First, an evaluation method in each example and comparative example will be described. In the evaluation of the positive photosensitive resin composition (hereinafter referred to as “varnish”), a varnish previously filtered with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

(1) Weight average molecular weight measurement The molecular weight of the polyamide resin was determined by using a GPC (gel permeation chromatography) apparatus (Waters 2690-996, manufactured by Nippon Waters Co., Ltd.) and using N-methyl-2-pyrrolidone (hereinafter referred to as NMP) as a developing solvent. The weight average molecular weight (Mw) was calculated in terms of polystyrene.

(2) Film thickness measurement The film thickness of the resin film on the substrate is measured using an optical interference type film thickness measuring device (Lambda Ace VM-1030 manufactured by Dainippon Screen Mfg. Co., Ltd.) with a refractive index of 1.629. did.

(3) Measurement of adhesion strength The adhesion strength with copper was measured by the following method.

First, copper was sputtered onto a silicon wafer to prepare a sputter substrate on which copper was formed with a thickness of 200 nm. On this substrate, varnish was applied by spin coating using a spinner (Mikasa Co., Ltd.) and then baked at 120 ° C. for 3 minutes using a hot plate (D-SPIN manufactured by Dainippon Screen Mfg. Co., Ltd.). A pre-baked film having a thickness of 8 to 10 μm was prepared. The reticle from which the pattern was cut was set in an exposure machine i-line stepper (NSR-2005i9C manufactured by Nikon Corporation), and exposed for 12 shots at an exposure amount of 500 mJ / cm ² . After exposure, the film was developed by a dip method using a tetramethylammonium aqueous solution (manufactured by Tama Chemical Co., Ltd.) diluted to 0.8% by weight with pure water, then rinsed with pure water, and a film thickness of 7 μm A positive pattern was obtained. Using a clean oven (CLH-21CD-S, manufactured by Koyo Thermo System Co., Ltd.), the patterned substrate was heated at 140 ° C. for 30 minutes under a nitrogen stream (oxygen concentration of 20 ppm or less), then further heated to 320 ° C. And cured for 1 hour to cure the polyimide pattern. Using the optical microscope of the optical interference film thickness measuring apparatus, the length and width of a rectangular convex pattern with a length of 30 μm and a width of 120 μm were measured, and the contact area with the substrate was calculated. The substrate was divided into two, and one substrate was subjected to a heating and humidification test for 100 hours at 85 ° C. and 85% RH using a constant temperature and humidity chamber (HAST CHAMBER EHS-221MD manufactured by Tabai Espec Co., Ltd.). Using a die shear tester (DAGE SERIES 4000, manufactured by Daisy Japan Co., Ltd.), a rectangular convex pattern with a length of 30 μm and a width of 120 μm was tested with a test height of 1 μm and a range of 2.5 N. Then, the operation of shearing and peeling in the vertical direction was performed for each of the five convex patterns of the same size, and the adhesion strength with the substrate was obtained from the average value and the pattern area. For any of the substrates, the adhesion strength was 60 MPa or more as good and less than 60 MPa as bad.

[Synthesis Example 1] Synthesis of diamine compound 52.9 g (0.15 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (hereinafter referred to as BAHF) was added to 300 mL of acetone and 52. It was dissolved in 3 g (0.9 mol) and cooled to -15 ° C. A solution prepared by dissolving 61.2 g (0.33 mol) of 3-nitrobenzoyl chloride in 300 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.

  90 g of solid was placed in a 1 L stainless steel autoclave, dispersed in 750 mL of methyl cellosolve, and 3 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 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, filtration was performed to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a diamine compound represented by the following formula.

[Synthesis Example 2] Synthesis of Polyamide Resin (A-1) Under a dry nitrogen stream, bis (3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA, manufactured by Manac Co., Ltd.) 6.20 g (0 .02 mol) was dissolved in 50 g of NMP. 9.67 g (0.016 mol) of the diamine compound obtained in Synthesis Example 1 and 0.37 g (0.002 mol) of benzoguanamine are added together with 10 g of NMP, and reacted at 20 ° C. for 1 hour. Reacted for hours. Next, 0.44 g (0.004 mol) of 3-aminophenol as an end-capping agent was added together with 5 g of NMP and reacted at 50 ° C. for 2 hours. Thereafter, a solution prepared by diluting 4.77 g (0.04 mol) of N, N-dimethylformamide dimethylacetal with 10 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of stirring, the solution was cooled to room temperature, and then the solution was poured into 1 L of water to obtain a precipitate. This precipitate was collected by filtration, washed with water three times, and then dried for 20 hours in a vacuum dryer at 80 ° C. to obtain a polyamide resin (A-1) powder. As a result of evaluation by the above method, the weight average molecular weight of the resin (A-1) was 26700. Moreover, it is p / (p + q) = 0.89 from the molar ratio of diamine.

[Synthesis Example 3] Synthesis of polyamide resin (A-2) Except for changing the diamine to 8.46 g (0.014 mol) of the diamine compound obtained in Synthesis Example 1 and 0.75 g (0.004 mol) of benzoguanamine. A polymerization reaction was performed in the same manner as in Synthesis Example 2 to obtain a polyamide resin (A-2) powder. The weight average molecular weight of the resin (A-2) was 19100. Moreover, it is p / (p + q) = 0.78 from the molar ratio of diamine.

[Synthesis Example 4] Synthesis of Polyamide Resin (A-3) The diamine was end-capped with 7.86 g (0.013 mol) of the diamine compound obtained in Synthesis Example 1 and 1.12 g (0.006 mol) of benzoguanamine. A polymerization reaction was carried out in the same manner as in Synthesis Example 2 except that the agent was changed to 0.22 g (0.002 mol) of 3-aminophenol to obtain a polyamide resin (A-3) powder. The weight average molecular weight of the resin (A-3) was 14600. Moreover, it is p / (p + q) = 0.68 from the molar ratio of diamine.

[Synthesis Example 5] Synthesis of Polyamide Resin (A-4) Diamine as BAHF 5.49 g (0.015 mol) and benzoguanamine 0.75 g (0.004 mol), and terminal blocking agent as 3-aminophenol 0.22 g A polymerization reaction was performed in the same manner as in Synthesis Example 2 except that the amount was changed to (0.002 mol) to obtain a polyamide resin (A-4) powder. The weight average molecular weight of the resin (A-4) was 13300. Moreover, it is p / (p + q) = 0.79 from the molar ratio of diamine.

[Synthesis Example 6] Synthesis of polyamide resin (A-5) The diamine was end-capped with 9.07 g (0.015 mol) of the diamine compound obtained in Synthesis Example 1 and 0.50 g (0.004 mol) of acetoguanamine. A polymerization reaction was carried out in the same manner as in Synthesis Example 2 except that the stopper was changed to 0.22 g (0.002 mol) of 3-aminophenol to obtain a polyamide resin (A-5) powder. The weight average molecular weight of the resin (A-5) was 20,100. Moreover, it is p / (p + q) = 0.79 from the molar ratio of diamine.

[Synthesis Example 7] Synthesis of Polyamide Resin (A-6) The polymerization reaction was carried out in the same manner as in Synthesis Example 2, except that the diamine was changed to 10.88 g (0.018 mol) of the diamine compound obtained in Synthesis Example 1. Then, a polyamide resin (A-6) powder was obtained. The weight average molecular weight of the resin (A-6) was 42900. Moreover, it is p / (p + q) = 1.00 from the molar ratio of diamine.

[Synthesis Example 8] Synthesis of Polyamide Resin (A-7) To 10.88 g (0.018 mol) of the diamine compound obtained in Synthesis Example 1 as a diamine, 5-amino-1H-tetrazole was added as a terminal blocking agent. A polymerization reaction was performed in the same manner as in Synthesis Example 2 except that the amount was changed to 34 g (0.004 mol) to obtain a polyamide resin (A-7) powder. The weight average molecular weight of Resin (A-7) was 37900. Moreover, it is p / (p + q) = 1.00 from the molar ratio of diamine.

[Synthesis Example 9] Synthesis of Polyamide Resin (A-8) The diamine was end-capped with 6.05 g (0.010 mol) of the diamine compound obtained in Synthesis Example 1 and 1.68 g (0.009 mol) of benzoguanamine. A polymerization reaction was performed in the same manner as in Synthesis Example 2 except that the agent was changed to 0.22 g (0.002 mol) of 3-aminophenol, to obtain a polyamide resin (A-8) powder. The weight average molecular weight of the resin (A-8) was 10700. Moreover, it is p / (p + q) = 0.53 from the molar ratio of diamine.

[Synthesis Example 10] Synthesis of quinonediazide compound Under a dry nitrogen stream, 12.74 g (0.03 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinonediazidesulfonyl chloride (NAC-5, 22.57 g (0.084 mol) manufactured by Toyo Gosei Co., Ltd. was dissolved in 300 g of 1,4-dioxane. While cooling the reaction vessel with ice, a liquid in which 50 g of 1,4-dioxane and 9.11 g (0.09 mol) of triethylamine were mixed was added dropwise so that the temperature in the system would not exceed 35 ° C. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into 2 L of water to obtain a precipitate. The precipitate was collected by filtration and further washed with 1 L of 1 wt% hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum drier to obtain a quinonediazide compound (B-1) represented by the following formula in which 2.8 of Q on average were converted to 5-naphthoquinonediazidesulfonic acid ester.

  (C) Thermal crosslinker NIKALAC (registered trademark) MX-270 (manufactured by Sanwa Chemical Co., Ltd.) used in the examples is shown below.

[Production of varnish]
Each component was put into a polypropylene vial with a capacity of 32 mL according to the composition shown in Table 1, and mixed using a stirring defoaming device ARE-310 (manufactured by Shinky Co., Ltd.) under the conditions of stirring for 10 minutes and defoaming for 1 minute. W-1 to 9) were prepared. In Table 1, “GBL” represents γ-butyrolactone. Regarding the varnish (W-9), the resin (A-8) was poorly soluble in GBL and became a suspension, which was not suitable for use. Varnishes (W-1 to 8) were filtered by the above method to remove fine foreign matters and used for evaluation.

[Examples 1-5, Comparative Examples 1-3]
Using the prepared varnish, the adhesion strength was measured by the above method. The results are shown in Table 2. In Comparative Examples 1 to 3, the adhesion strength to the copper sputter substrate after the heating and humidification test was insufficient. In Comparative Example 2, cracks were observed in a part of the pattern after the heating and humidification test.

Claims (4)

(A) The sum of the number of structural units represented by the general formula (1) and the number of structural units represented by the general formula (2) is 50% or more of the total number of structural units, and is represented by the general formula (1). P / (p + q) = 0.60 to 0.95, (b) a quinonediazide compound, (c) where p is the number of structural units to be represented and q is the number of structural units represented by the general formula (2) A positive photosensitive resin composition comprising a thermal crosslinking agent and (d) a solvent.

(In General Formulas (1) and (2), X is a divalent to tetravalent organic group having 3 to 40 carbon atoms, and the group represented by X— (R ¹ ) _m is the following (Z-1): What is not included in the group, Y is a divalent to hexavalent organic group having 4 to 40 carbon atoms, Z is one or more groups selected from the following group (Z-1): R ¹ is the same or different. at best, .R ² showing a hydroxyl group or ^{O-R 3} may be the same or different, a hydroxyl group, a carboxyl group, .R ³ showing the ^{O-R 3} or ^{COO-R 3} is 1 to 15 carbon atoms An organic group, and either R ¹ or R ² contains a hydroxyl group or a carboxyl group, m is an integer of 0-2, n is an integer of 0-4, and m + n> 1.

(R ⁴ represents a hydrogen atom, a hydroxyl group, a mercapto group, or a monovalent hydrocarbon group having 1 to 10 carbon atoms.) X in the general formula (1) is one or more groups selected from the following group (X-1), and Y in the general formulas (1) and (2) is selected from the following (Y-1) group. The positive photosensitive resin composition according to claim 1, wherein the positive photosensitive resin composition is one or more groups.

(In the formula, when a plurality of R ⁵ are present, they may be the same or different, and one or more groups or atoms selected from an alkyl group having 1 to 10 carbon atoms, an alkyl ester group having 2 to 10 carbon atoms and a halogen atom) R is an integer of 0 to 4)

(In the formula, when two R ⁷ are present, they may be the same or different and each represents one or more groups or atoms selected from an alkyl group having 1 to 10 carbon atoms and a halogen atom. It is an integer. The positive photosensitive resin according to claim 1 or 2, wherein 20 to 100% of X in the general formula (1) is one or more groups selected from the following group (X-2). Composition.

Z in the said General formula (2) is represented by General formula (3), The positive photosensitive resin composition in any one of Claims 1-3 characterized by the above-mentioned.

(R ⁴ represents a hydrogen atom, a hydroxyl group, a mercapto group, or a monovalent hydrocarbon group having 1 to 10 carbon atoms.)