JP4760026B2 - Positive photosensitive resin composition, semiconductor device and display element using the positive photosensitive resin composition, and manufacturing method of semiconductor device and display element - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a semiconductor device and a display element using the positive photosensitive resin composition, and a method for manufacturing the semiconductor device and the display element.

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. On the other hand, in order to simplify the process, a positive photosensitive resin in which the polybenzoxazole resin or polyimide resin is combined with a diazoquinone compound as a photosensitive material is also used (for example, see Patent Document 1). In recent years, due to miniaturization of semiconductor elements, multi-layer wiring by high integration, shift to chip size package (CSP), wafer level package (WLP), etc., it is processed with various chemicals in the wafer process step. It has become. In these new packages, the conventional wire bonding is moving to a form using bumps. Normally, when mounting bumps, flux is used for reflow. At this time, the cured film of the positive type photosensitive resin is in direct contact with the flux, and at that time, wrinkles and cracks are often positive. Development of a positive photosensitive resin composition excellent in reflow resistance is strongly desired. Also, in the field of display elements, various chemical solutions are used in the manufacturing process, and there is a problem that the same problems as described above occur during the process, and a positive photosensitive material with excellent solvent resistance is required. It is coming.
Japanese Examined Patent Publication No. 1-46862

  The present invention provides a positive photosensitive resin composition excellent in reflow resistance and solvent resistance, a semiconductor device, and a display element.

Such an object is achieved by the present invention described in the following [1] to [10].
[1] A polyamide resin (A) having a molecular terminal and an unsaturated group in the molecule, and a diazoquinone compound (B), and the polyamide resin (A) is a polybenzoxazole precursor structure, a polyamic acid structure or a polyamic acid ester A positive-type photosensitive resin composition characterized by containing one or two or more structures.
[2] The polyamide resin (A) has a structure represented by the general formula (1), and the unsaturated group in the molecule in the general formula (1) is represented by the general formula (2) -1, (2) -2, The positive photosensitive resin composition according to item [1], wherein the positive photosensitive resin composition is selected from organic groups having a structure represented by:

[3] A positive photosensitive resin composition in which the organic group described in the item [2] is 0.1 to 70 mol% in the total amount of Y in the general formula (1).
[4] Item [1], [2] or [3], wherein the unsaturated group in the molecule of the polyamide resin (A) represented by the general formula (1) is selected from organic groups having the following structure: Positive photosensitive resin composition.

[5] Item [1], [2], [3] or [4], wherein the unsaturated group at the molecular end of the polyamide resin represented by formula (1) is selected from organic groups having the following structure: A positive photosensitive resin composition.

[6] A step of coating the positive photosensitive resin composition according to any one of claims 1 to 5 on a substrate to form a composition layer, and irradiating active energy rays to the approximate composition layer. And a step of forming a pattern by contacting with a developing solution, and a step of heating the approximate composition.

[7] A semiconductor device manufactured using the positive photosensitive resin composition according to any one of claims 1 to 5.

[8] A display element produced by using the positive photosensitive resin composition according to any one of claims 1 to 5.

[9] The positive photosensitive resin composition according to any one of claims 1 to 5 is obtained by patterning on a semiconductor element so that a film thickness after heating becomes 0.1 to 30 μm. A method for manufacturing a semiconductor device.

[10] The positive photosensitive resin composition according to any one of claims 1 to 5 is patterned on a display element substrate so that a film thickness after heating is 0.1 to 30 μm. A method for producing a display element obtained by the method.

  According to the present invention, a positive photosensitive resin composition excellent in reflow resistance and solvent resistance, and a semiconductor device and a display element using the same can be obtained.

  As the polyamide resin having an unsaturated group in the molecule terminal and molecule used in the present invention, it is a polybenzoxazole precursor structure, a polyamic acid structure or a polyamic acid ester structure, and a hydroxyl group, a carboxyl group, Or it is resin which has a sulfonic acid group. Among these, a polyamide resin including a structure represented by the general formula (1) is preferable from the viewpoint of heat resistance after the final heating. Further, some of these resins may be ring-closed to have a polybenzoxazole structure or a polyimide structure.

X of the polyamide resin having the structure represented by the general formula (1) represents a divalent to tetravalent organic group, R ₁ is a hydroxyl group or O—R ₃ , and m is an integer of 0 to 2. . Each R ₁ may be the same or different. Y in the general formula (1) represents a divalent to hexavalent organic group, R ₂ is a hydroxyl group, a carboxyl group, O—R ₃ or COO—R ₃ , and n is an integer of 0 to 4. Each R ₂ may be the same or different. Here, R ₃ is an organic group having 1 to 15 carbon atoms. However, when R ₁ has no hydroxyl group, at least one R ₂ must be a carboxyl group. When R ₂ has no carboxyl group, at least one R ₁ must be a hydroxyl group.

  The polyamide resin having a molecular terminal and an unsaturated group in the molecule of the present invention preferably has a structure represented by the general formula (1), and the unsaturated group in the molecule in the general formula (1) is represented by the general formula ( A structure represented by 2) is preferred. More preferably, the structure represented by the general formula (2) in the total amount of Y in the general formula (1) is 0.1 mol% or more and 70 mol% or less. If it is less than the lower limit, the effect of reflow resistance is not observed. Moreover, since the tensile elongation of a cured film will fall when it exceeds an upper limit, it is not preferable.

As an unsaturated group in the molecule | numerator of the polyamide resin which has a structure shown by General formula (1) used by this invention, for example, a structure shown by General formula (2)

等であるが、これらに限定されるものではない。

However, it is not limited to these.

Among these, preferred are those having the structures shown below.

  The polyamide resin containing the structure represented by the general formula (1) is, for example, a compound selected from diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, etc. and a general formula having a structure of Y ( 2) It is obtained by reacting a compound selected from tetracarboxylic acid anhydride, trimellitic acid anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, and the like. In the case of dicarboxylic acid, an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

In the polyamide resin containing the structure represented by the general formula _{(1), O-R 3} , COO-R 3 as a substituent of O-R _3, Y as a substituent of X is a hydroxyl group, an alkaline aqueous solution of the carboxyl group Is a group protected by R ₃ which is an organic group having 1 to 15 carbon atoms, and if necessary, a hydroxyl group or a carboxyl group may be protected. 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 250 to 400 ° C., it is dehydrated and closed, and a heat-resistant resin is obtained in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both.

等であるが、これらに限定されるものではない。 As X in the general formula (1), for example,

However, it is not limited to these.

より選ばれるものであり、又２種類以上用いても良い。 Among these, particularly preferred are:

Two or more types may be used.

As Y in the general formula (1), in addition to the general formula (2), for example,

等であるが、これらに限定されるものではない。

However, it is not limited to these.

Among these, particularly preferred are:

Two or more types may be used.

  In the present invention, the end of the polyamide resin is sealed. Although it is known that end-capping is effective for the storage stability of a positive photosensitive resin, this time, it is characterized in that an unsaturated group is introduced into the polyamide resin and an unsaturated group is also introduced into the end. For sealing, a derivative having an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group can be introduced as an acid derivative or an amine derivative at the end of the polyamide represented by the general formula (1). Specifically, for example, a compound selected from diamine or bis (aminophenol) having a structure of X, 2,4-diaminophenol, and the like, and a tetracarboxylic acid anhydride, trimellitic acid anhydride, dicarboxylic acid having a structure of Y After synthesizing a polyamide resin having a structure represented by the general formula (1) obtained by reacting with a compound selected from acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, etc. It is preferable to cap the terminal amino group contained in the polyamide resin as an amide using an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. Examples of the group derived from an acid anhydride or acid derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group after reacting with an amino group include:

等が挙げられるが、これらに限定されるものではない。

However, it is not limited to these.

Among these, particularly preferred are:

Two or more types may be used. The method is not limited to this method, and the terminal acid contained in the polyamide resin is capped as an amide using an amine derivative containing an aliphatic group or cyclic compound group having at least one alkenyl group or alkynyl group. You can also

  The diazoquinone compound (B) used in the present invention is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is a substance known from U.S. Pat. It is. For example, the following are mentioned.

  Among these, an ester of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid is particularly preferable. Examples of these include, but are not limited to, the following. Two or more of these may be used.

  The preferable addition amount of the diazoquinone compound (B) used in the present invention is 1 to 50 parts by weight with respect to 100 parts by weight of the polyamide resin. If the amount is less than 1 part by weight, a good pattern cannot be obtained, and if it exceeds 50 parts by weight, the sensitivity is greatly reduced.

If necessary, additives such as a leveling agent, a silane coupling agent, a titanate coupling agent, and their respective reactants can be added to the positive photosensitive resin composition in the present invention.
The polyamide resin of the present invention is dissolved in a solvent and used in the form of a varnish. Solvents include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropio And the like, and may be used alone or in combination.

  In the method of using the positive photosensitive resin composition of the present invention, first, the composition is applied to a suitable support such as a silicon wafer, a ceramic substrate, an aluminum substrate and the like. In the case of a semiconductor device, the coating amount is applied so that the final film thickness after curing is 0.1 to 30 μm. If the film thickness is below the lower limit value, it will be difficult to fully function as a surface protection film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern as well as processing. Takes a long time to reduce throughput. Examples of the coating method include spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, and the like. Next, after prebaking at 60 to 130 ° C. to dry the coating film, actinic radiation is applied to the desired pattern shape. As the actinic radiation, 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 preferable.

  Next, a relief pattern is obtained by dissolving and removing the irradiated portion with a developer. Developers include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine, and di-n. Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium such as tetramethylammonium hydroxide and tetraethylammonium hydroxide An aqueous solution of an alkali such as a salt and an aqueous solution to which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added can be preferably used. As a developing method, methods such as spraying, paddle, dipping, and ultrasonic waves are possible.

  Next, the relief pattern formed by development is rinsed. Distilled water is used as the rinse liquid. Next, heat treatment is performed to form an oxazole ring and / or an imide ring, thereby obtaining a final pattern rich in heat resistance.

  The photosensitive resin composition according to the present invention is useful not only for semiconductor applications, but also for interlayer insulation of multilayer circuits, flexible copper-clad cover coats, solder resist films, liquid crystal alignment films, and display devices.

  Examples of specific uses for semiconductors include a passivation film obtained by forming the above-described photosensitive resin composition film on a semiconductor element, and a photosensitive resin composition described above on a passivation film formed on a semiconductor element. Examples thereof include a buffer coat film formed by forming a physical film, and an interlayer insulating film formed by forming the above-described photosensitive resin composition film on a circuit formed on a semiconductor element.

  Among them, as one application example in which the photosensitive resin composition of the present invention is used in a semiconductor device, application to a semiconductor device having bumps will be described with reference to the drawings. FIG. 1 is an enlarged sectional view of a pad portion of a semiconductor device having a bump according to the present invention. As shown in FIG. 1, a passivation film 3 is formed on an input / output Al pad 2 in a silicon wafer 1, and a via hole is formed in the passivation film 3. Further, a positive photosensitive resin (buffer coating film) 4 is formed thereon, and a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and the metal film 5 is formed of solder bumps. 9 is etched to insulate between the pads. Barrier metal 8 and solder bumps 9 are formed on the insulated pads.

  Examples of display device applications include TFT interlayer insulating films, TFT element flattening films, color filter flattening films, protrusions for MVA liquid crystal display devices, and cathode partitions for organic EL elements. The usage method is based on forming the photosensitive resin composition layer patterned on the board | substrate which formed the display body element and the color filter by said method according to a semiconductor use. High transparency is required for display device applications, especially interlayer insulation films and planarization films, but by introducing a post-exposure process before curing the photosensitive resin composition layer, it is excellent in transparency. A resin layer can be obtained, which is more preferable in practical use.

<< Production Example 1 >>
[Production of 5-ethynylisophthalic acid dichloride]
(1) Synthesis of dimethyl 5-trifluoromethanesulfonyloxyisophthalate 190.0 g of dimethyl 5-hydroxyisophthalate was added to a four-necked 5 L flask equipped with a thermometer, a Dimro condenser tube, a calcium chloride tube, and a stirrer. 0.904 mol), 3 L of dehydrated toluene, and 214.7 g (2.718 mol) of dehydrated pyridine were charged and cooled to −30 ° C. with stirring. Here, 510.2 g (1.808 mol) of trifluoromethanesulfonic anhydride was slowly added dropwise while taking care not to increase the temperature to -25 ° C or higher. In this case, it took 1 hour to complete the dropping. After completion of the dropwise addition, the reaction temperature was raised to 0 ° C. for 1 hour, and further raised to room temperature for 5 hours. The obtained reaction mixture was poured into 4 L of ice water, and the aqueous layer and the organic layer were separated. Furthermore, the aqueous layer was extracted twice with 500 mL of toluene, and this was combined with the previous organic layer. This organic layer was washed twice with 3 L of water, dried with 100 g of anhydrous magnesium sulfate, filtered to remove anhydrous magnesium sulfate, toluene was distilled off with a rotary evaporator, and dried under reduced pressure. 294.0 g of dimethyl trifluoromethanesulfonyloxyisophthalate was obtained (yield 95%). The crude product was recrystallized from hexane to obtain white needle crystals, which were used for the next reaction.

(2) Synthesis of 4- [3,5-bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol Four equipped with a thermometer, a Dimroth condenser, a dry nitrogen inlet, and a stirrer In a 1 L flask at the neck, 125 g (0.365 mol) of dimethyl 5-trifluoromethanesulfonyloxyisophthalate obtained in (1) above, 1.1 g (0.00419 mol) of triphenylphosphine, 0.275 g of copper iodide ( 0.00144 mol) and 3-methyl-1-butyn-3-ol 33.73 g (0.401 mol) were charged and nitrogen was allowed to flow. 375 mL of dehydrated triethylamine and 200 mL of dehydrated pyridine were added and dissolved by stirring. After continuing to flow nitrogen for 1 hour, 0.3 g (0.000427 mol) of dichlorobis (triphenylphosphine) palladium was quickly added and heated to reflux for 1 hour in an oil bath. Thereafter, triethylamine and pyridine were distilled off under reduced pressure to obtain a viscous brown solution. This was poured into 500 mL of water, and the precipitated solid was collected by filtration and further washed twice with 500 mL of water, 500 mL of 5 mol / L hydrochloric acid and 500 mL of water. The solid was dried under reduced pressure at 50 ° C. to obtain 98.8 g of 4- [3,5-bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol (yield) 98%).

(3) Synthesis of 5-ethynylisophthalic acid dipotassium salt In a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 3 L of n-butanol, 182 g of potassium hydroxide (85%) (2.763 mol) ) And heated to reflux to dissolve. To this was added 95 g (0.344 mol) of 4- [3,5-bis (methoxycarbonyl) phenyl] -2-methyl-3-butyn-1-ol synthesized in (2) above, and the mixture was heated under reflux for 30 minutes. did. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. The crystals were washed twice with 1 L of ethanol and dried under reduced pressure at 60 ° C. to obtain 88.87 g of dipotassium 5-ethynylisophthalate (yield 97%).

(4) Synthesis of 5-ethynylisophthalic acid dichloride Into a 2 L 4-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 80 g of dipotassium 5-ethynylisophthalic acid obtained in (3) above (0 .3 mol) and 400 L of chloroform were charged and cooled to 0 ° C. To this, 391 g (4.5 mol) of thionyl chloride was added dropwise at 5 ° C. or less over 1 hour. Thereafter, 4 mL of dimethylformamide and 4 g of hydroquinone were added, and the mixture was stirred at 45 to 50 ° C. for 3 hours. After cooling, the mixture was filtered to remove crystals, and the crystals were washed with 150 mL of chloroform. The filtrate and the washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the resulting residue was extracted and filtered twice with 200 mL of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semisolid crude product. This was washed with dry n-hexane and then recrystallized with diethyl ether to obtain 13 g of 5-ethynylisophthalic acid dichloride (yield 19%).
Further, in the production of 5-ethynylisophthalic acid dichloride, 5-ethynylterephthalic acid dichloride was produced in the same manner except that dimethyl 5-hydroxyisophthalate was replaced with dimethyl 5-hydroxyterephthalate. 4-Ethynyl-2,6-naphthalenedicarboxylic acid dichloride was produced in the same manner except that dimethyl hydroxyisophthalate was replaced with dimethyl 4-hydroxy-2,6-naphthalenedicarboxylate.

<< Production Example 2 >>
[Production of 5-phenylethynylisophthalic acid dichloride]
(1) Synthesis of 5-bromoisophthalic acid 99.18 g (0.55 mol) of 5-aminoisophthalic acid and 48% by weight of hydrobromic acid were added to a 4-neck 1 L flask equipped with a thermometer, a stirrer and a dropping funnel. 165 mL and distilled water 150 mL were added and stirred. The flask was cooled to 5 ° C. or lower, and sodium nitrite 39.4 g (0.57 mol) dissolved in distilled water 525 mL was added dropwise over 1 hour to obtain a diazonium salt aqueous solution. 94.25 g (0.66 mol) of cuprous bromide and 45 mL of 48 wt% hydrobromic acid were placed in a 4 L 3 L flask equipped with a thermometer, a Dimroth condenser, a dropping funnel and a stirrer and stirred. . The flask was cooled to 0 ° C. or lower, and the diazonium salt aqueous solution was added dropwise over 2 hours. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes and then refluxed for 30 minutes. After allowing to cool, the precipitate was separated by filtration and washed twice with 2 L of distilled water, and the resulting white solid was dried under reduced pressure at 50 ° C. for 2 days to obtain 117 g of a crude product. Used in the next reaction without purification.

(2) Synthesis of dimethyl 5-bromoisophthalate 110 g of 5-bromoisophthalic acid obtained in (1) above, 500 mL of methanol, and 10 g of concentrated sulfuric acid were placed in a 500 mL flask equipped with a stirrer and a Dimroth condenser. Refluxed. After standing to cool, it was added dropwise to 1 L of distilled water and neutralized with a 5 wt% aqueous sodium hydrogen carbonate solution. The precipitate was separated by filtration and washed twice with 2 L of distilled water, and the obtained white solid was dried under reduced pressure at 50 ° C. for 2 days to obtain 109 g (0.4 mol) of dimethyl 5-bromoisophthalate ( Yield 89%).

(3) Synthesis of 5-phenylethynylisophthalic acid dichloride In Production Example 1 (2), 125 g (0.365 mol) of dimethyl 5-trifluoromethanesulfonyloxyisophthalate was converted to 5-bromoisophthalic acid obtained in (2) above. 80.8 g of 1- [3,5-bis (methoxycarbonyl) phenyl] -2-phenylethyne was obtained in the same manner except for using 99.7 g (70.365 mol) of dimethyl acid (yield 75%). .
Thereafter, in the same manner as in Production Examples 1 (3) and (4), 5- (2-phenylethynyl) isophthalic acid dipotassium salt was obtained, and then 5- (2-phenylethynyl) isophthalic acid dichloride was obtained.

Example 1
[Synthesis of polyamide resin]
Hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (38.09 g, 0.104) was added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen inlet tube. Mol) was dissolved in 150 mL of dry N-methyl-2-pyrrolidone (NMP), and 17.47 g (0.173 mol) of triethylamine was further added to this solution. After the inside of the reaction vessel was kept at 5 ° C. or less under dry nitrogen, 15.28 g (0.052 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride, 7.84 g (0.035 mol) of 5-ethynylisophthalic acid dichloride, 50 g of N-methyl-2-pyrrolidone was added. Subsequently, the mixture was stirred at 5 ° C. or lower for 3 hours under the same dry nitrogen. Then, it returned to room temperature and stirred for 12 hours. Next, 5.98 g (0.036 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 20 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-1) was obtained.

[Preparation of resin composition]
10 g of the synthesized polyamide resin (A-1) and 2 g of diazoquinone compound (B-1) having the following structure are dissolved in 30 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter to form a positive photosensitive resin composition. I got a thing.

[Developability evaluation]
This positive photosensitive resin composition was applied to an 8-inch silicon wafer using a spin coater and then dried on a hot plate at 120 ° C. for 4 minutes to obtain a coating film having a thickness of about 7 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: remaining pattern and blank pattern with a width of 0.88 to 50 μm are drawn), Nikon Corporation i-line stepper NSR-4425i The exposure was performed by increasing the exposure amount in steps of 100 mJ / cm ² to 10 mJ / cm ² . Next, the development time was adjusted in a 2.38% tetramethylammonium hydroxide aqueous solution so that the film slip during development was 1.5 μm, and the exposed portion was dissolved and removed, followed by rinsing with pure water for 30 seconds. When the pattern was observed, it was confirmed that the pattern was satisfactorily opened without scum at an exposure amount of 300 mJ / cm ² .

[Reflow resistance evaluation]
The patterned wafer was cured by heat treatment in a clean oven at 150 ° C./30 minutes and 350 ° C./60 minutes in a nitrogen atmosphere. Next, a flux, BF-30, manufactured by Tamura Kaken Co., Ltd. was applied to the wafer with a spinner at 500 rpm / 30 seconds + 1000 rpm / 30 seconds. In a reflow furnace, it was passed twice under conditions of 140 to 160 ° C./100 seconds (preheating) and 320 ° C./30 seconds. Next, after washing with xylene for 10 minutes, it was rinsed with isopropyl alcohol and dried. When the film surface from which the flux had been removed was observed with a metallographic microscope, it was satisfactory with no occurrence of cracks, wrinkles and the like.

[Evaluation of film properties]
The positive photosensitive resin composition was applied to a bare silicon wafer so as to have a thickness of 10 μm after curing, and was cured by heat treatment in a clean oven at 150 ° C./30 minutes and 350 ° C./60 minutes in a nitrogen atmosphere. Next, using a dicing saw, it was cut into a strip having a width of 10 mm, the cut wafer was immersed in a 2% aqueous hydrofluoric acid solution, and the cured film was peeled off. After the obtained film was dried at 60 ° C. for 8 hours, the elongation was measured with a tensile test apparatus, and the elongation was as good as 32%.

Example 2
[Synthesis of polyamide resin]
Hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (38.09 g, 0.104) was added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen inlet tube. Mol) was dissolved in 150 mL of dry N-methyl-2-pyrrolidone (NMP), and 17.47 g (0.173 mol) of triethylamine was further added to this solution. After the inside of the reaction vessel was kept at 5 ° C. or lower under dry nitrogen, 15.28 g (0.052 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride, 10.47 g (0.035 mol) of 5-phenylethynylisophthalic acid dichloride. ), 50 g of N-methyl-2-pyrrolidone was added. Subsequently, the mixture was stirred at 5 ° C. or lower for 3 hours under the same dry nitrogen. Then, it returned to room temperature and stirred for 12 hours. Next, 5.98 g (0.036 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 20 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-2) was obtained.

[Production and development of resin composition, reflow resistance, evaluation of film properties]
Using the obtained polyamide resin (A-2), a resin composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
[Synthesis of polyamide resin]
Hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (38.09 g, 0.104) was added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen inlet tube. Mol) was dissolved in 150 mL of dry N-methyl-2-pyrrolidone (NMP), and 17.47 g (0.173 mol) of triethylamine was further added to this solution. After making the inside of the reaction vessel 5 ° C. or less under dry nitrogen, 7.64 g (0.026 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride, 13.72 g (0.060 mol) of 5-ethynylisophthalic acid dichloride. , 50 g of N-methyl-2-pyrrolidone was added. Subsequently, the mixture was stirred at 5 ° C. or lower for 3 hours under the same dry nitrogen. Then, it returned to room temperature and stirred for 12 hours. Next, 5.98 g (0.036 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 20 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-3) was obtained.

[Production and development of resin composition, reflow resistance, evaluation of film properties]
10 g of the obtained polyamide resin (A-3) and 1 g of a diazoquinone compound (B-2) having the following structure are dissolved in 30 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter to form a positive photosensitive resin. A composition was obtained. The developability, reflow resistance, and film physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 4
[Synthesis of polyamide resin]
30.47 g (0.083) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen inlet tube. Mol), 3,3-diamino-4,4′-dihydroxybiphenyl (4.50 g, 0.021 mol) was dissolved in 150 mL of dry N-methyl-2-pyrrolidone (NMP), and triethylamine was added to the solution. 17.47 g (0.173 mol) was added. After the inside of the reaction vessel was kept at 5 ° C. or less under dry nitrogen, 20.38 g (0.068 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride, 5.23 g (0.017 mol) of 5-phenylethynylisophthalic acid dichloride. , 50 g of N-methyl-2-pyrrolidone was added. Subsequently, the mixture was stirred at 5 ° C. or lower for 3 hours under the same dry nitrogen. Then, it returned to room temperature and stirred for 12 hours. Next, 6.19 g (0.036 mol) of 5-ethynyl-isobenzofuran-1,3-dione dissolved in 20 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-4) was obtained.

[Production and development of resin composition, reflow resistance, evaluation of film properties]
10 g of the obtained polyamide resin (A-3) and 2.8 g of a diazoquinone compound (B-3) having the following structure were dissolved in 30 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter, and positive photosensitive A functional resin composition was obtained. The developability, reflow resistance, and film physical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5
[Synthesis of polyamide resin]
30.47 g (0.083) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen inlet tube. Mol), 3,3-diamino-4,4′-dihydroxybiphenyl (4.50 g, 0.021 mol) was dissolved in 150 mL of dry N-methyl-2-pyrrolidone (NMP), and triethylamine was added to the solution. 17.47 g (0.173 mol) was added. After the inside of the reaction vessel was kept at 5 ° C. or less under dry nitrogen, 22.93 g (0.078 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride, 2.62 g (0.009 mol) of 5-phenylethynylisophthalic acid dichloride , 50 g of N-methyl-2-pyrrolidone was added. Subsequently, the mixture was stirred at 5 ° C. or lower for 3 hours under the same dry nitrogen. Then, it returned to room temperature and stirred for 12 hours. Next, 3.13 g (0.018 mol) of 5-ethynyl-isobenzofuran-1,3-dione dissolved in 20 g of N-methyl-2-pyrrolidone, 5-norbornene-2,3-dicarboxylic acid anhydride, 2. 99 g (0.018 mol) was added, and the mixture was further stirred for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-5) was obtained.

[Production and development of resin composition, reflow resistance, evaluation of film properties]
Using the obtained polyamide resin (A-5), a resin composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6
[Synthesis of polyamide resin]
A thermometer, a stirrer, and a raw material charging port were formed with 13.39 g (0.043 mol) of 4,4′-oxydiphthalic anhydride, 2.89 g (0.090 mol) of methanol, and 7.51 g (0.095 mol) of pyridine. Into a four-necked separable flask equipped with a dry nitrogen inlet tube, 150 g of N-methyl-2-pyrrolidone was added and dissolved, and the mixture was reacted at room temperature for 5 hours. To this reaction solution was added 10.47 g (0.088 mol) of thionyl chloride, and the mixture was stirred at room temperature for 5 hours. Next, 5.09 g (0.017 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride
30 g of N-methyl-2-pyrrolidone and 5.88 g (0.026 mol) of 5-ethynylisophthalic acid dichloride were added. Next, 38.09 g (0.104 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was added together with 70 g of N-methyl-2-pyrrolidone at 5 ° C. or less, and 5 ° C. or less. For 3 hours. Then, it returned to room temperature and made it react for 5 hours. Next, 5.98 g (0.036 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 20 g of N-methyl-2-pyrrolidone is added, and the temperature is raised to 75 ° C. in an oil bath, and further 5 The reaction was terminated by stirring for a period of time. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-6) was obtained.

[Production and development of resin composition, reflow resistance, evaluation of film properties]
After dissolving in 10 g of synthesized polyamide resin (A-6), 2 g of diazoquinone compound (B-1) having the following structure, and 30 g of γ-butyrolactone, it is filtered through a 0.2 μm fluororesin filter, and is a positive photosensitive resin. A composition was obtained. This positive photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 7
[Synthesis of polyamide resin]
A thermometer, a stirrer, and a raw material charging port were charged with 13.39 g (0.043 mol) of 4,4′-oxydiphthalic anhydride, 2.89 g (0.090 mol) of methanol and 7.11 g (0.090 mol) of pyridine. Into a four-necked separable flask equipped with a dry nitrogen inlet tube, 150 g of N-methyl-2-pyrrolidone was added and dissolved, and the mixture was reacted at room temperature for 5 hours. To this reaction solution was added 10.47 g (0.088 mol) of thionyl chloride, and the mixture was stirred at room temperature for 5 hours. Next, 5.36 g (0.017 mol) of 4,4′-oxydiphthalic anhydride, 7.85 g (0.026 mol) of 5-phenylethynylisophthalic acid dichloride, and 30 g of N-methyl-2-pyrrolidone were added. The reaction solution was synthesized according to JP-A-3-200722, and 62.87 g (0.002 g) of bis-N, N ′-(p-aminobenzoyl) -hexafluoro-2,2-bis (4-hydroxyphenyl) propane having the following structure was synthesized. 104 mol), 80 g of N-methyl-2-pyrrolidone was added at 10 ° C. or less, and the mixture was allowed to react for 3 hours, then returned to room temperature and further reacted overnight. Next, 5.98 g (0.036 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 20 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-7) was obtained.

[Production and development of resin composition, reflow resistance, evaluation of film properties]
After dissolving in 10 g of synthesized polyamide resin (A-7), 2 g of diazoquinone compound (B-1) having the following structure, and 30 g of γ-butyrolactone, it is filtered through a 0.2 μm fluororesin filter, and is a positive photosensitive resin. A composition was obtained. This positive photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<< Comparative Example 1 >>
[Synthesis of polyamide resin]
Hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (38.09 g, 0.104) was added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen inlet tube. Mol) was dissolved in 150 mL of dry N-methyl-2-pyrrolidone (NMP), and 17.47 g (0.173 mol) of triethylamine was further added to this solution. After the inside of the reaction vessel was kept at 5 ° C. or lower under dry nitrogen, 12.74 g (0.043 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride, 8.73 g (0.043 mol) of isophthalic acid dichloride, N-methyl 2-Pyrrolidone 50g was added. Subsequently, the mixture was stirred at 5 ° C. or lower for 3 hours under the same dry nitrogen. Then, it returned to room temperature and stirred for 12 hours. Next, 5.98 g (0.036 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 20 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-8) was obtained.
[Production and development of resin composition, reflow resistance, evaluation of film properties]
After dissolving in 10 g of the synthesized polyamide resin (A-8), 2 g of photosensitive diazoquinone (B-2) having the following structure and 30 g of γ-butyrolactone, it was filtered through a 0.2 μm fluororesin filter, and positive photosensitive A resin composition was obtained. This positive photosensitive resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

<< Comparative Example 2 >>
[Synthesis of polyamide resin]
30.47 g (0.083) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane was added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen inlet tube. Mol), 3,3-diamino-4,4′-dihydroxybiphenyl (4.50 g, 0.021 mol) was dissolved in 150 mL of dry N-methyl-2-pyrrolidone (NMP), and triethylamine was added to the solution. 17.47 g (0.173 mol) was added. After the inside of the reaction vessel was kept at 5 ° C. or lower under dry nitrogen, 25.47 g (0.086 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride and 50 g of N-methyl-2-pyrrolidone were added. Subsequently, the mixture was stirred at 5 ° C. or lower for 3 hours under the same dry nitrogen. Then, it returned to room temperature and stirred for 12 hours. Next, 5.98 g (0.036 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 20 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 5 hours to complete the reaction. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-9) was obtained.

[Production and development of resin composition, reflow resistance, evaluation of film properties]
Using the obtained polyamide resin (A-9), a resin composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<< Comparative Example 3 >>
[Synthesis of polyamide resin]
Hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (38.09 g, 0.104) was added to a four-necked separable flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen inlet tube. Mol) was dissolved in 150 mL of dry N-methyl-2-pyrrolidone (NMP), and 17.47 g (0.173 mol) of triethylamine was further added to this solution. After making the inside of the reaction vessel 5 ° C. or less under dry nitrogen, 15.28 g (0.052 mol) of diphenyl ether-4,4′-dicarboxylic acid chloride, 7.84 g (0.035 mol) of 5-ethynylisophthalic acid dichloride. , 50 g of N-methyl-2-pyrrolidone was added. Subsequently, the mixture was stirred at 5 ° C. or lower for 3 hours under the same dry nitrogen. Then, it returned to room temperature and stirred for 12 hours. After filtering the reaction mixture, the reaction mixture was poured into a solution of water / methanol = 3/1 (volume ratio), the precipitate was collected by filtration, washed thoroughly with water, dried under vacuum, and the desired polyamide resin ( A-10) was obtained.
[Production and development of resin composition, reflow resistance, evaluation of film properties]
Using the obtained polyamide resin (A-10), a resin composition was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 1.

  INDUSTRIAL APPLICABILITY The present invention provides a positive photosensitive resin composition that is highly sensitive and can be patterned without scum, and can be suitably used for a surface protective film, an interlayer insulating film, and the like of semiconductor elements and display elements.

The expanded sectional view of the pad part of an example of the semiconductor device which has a bump of the present invention is shown.

Explanation of symbols

1 Silicon wafer 2 Al pad 3 Passivation film 4 Buffer coat film 5 Metal (Cr, Ti, etc.) film 6 Wiring (Al, Cu, etc.)
7 Insulating film 8 Barrier metal 9 Solder bump

Claims (10)

Polyamide resin (A) having a terminal end and an unsaturated group in the molecule, and a diazoquinone compound (B), wherein the polyamide resin (A) is a polybenzoxazole precursor structure, a polyamic acid structure or a polyamic acid Each of the ester structures contains one or more kinds of ester structures, and the unsaturated group in the molecule of the polyamide resin (A) is an unsaturated group having a structure excluding the unsaturated bond in the benzene ring , and the polyamide resin ( The unsaturated group at the molecular end of A) is introduced as a result of terminal modification , and the unsaturated group at the molecular end of the polyamide resin (A) is selected from organic groups having the following structure. A positive-type photosensitive resin composition.

The polyamide resin (A) has a structure represented by the general formula (1), and the unsaturated group in the molecule in the general formula (1) is selected from organic groups having a structure represented by the general formula (2). The positive photosensitive resin composition according to claim 1.

  The positive photosensitive resin composition whose organic group of Claim 2 is 0.1-70 mol% among the total amount of Y in General formula (1). The positive photosensitive resin composition according to claim 2 or 3, wherein the unsaturated group in the molecule of the polyamide resin (A) represented by the general formula (1) is selected from organic groups having the following structure.

The positive photosensitive resin composition according to any one of claims 1 to 4 , wherein the unsaturated group at the molecular terminal of the polyamide resin represented by the general formula (1) is selected from organic groups having the following structure.

A step of applying the positive photosensitive resin composition according to any one of claims 1 to 5 on a substrate to form a composition layer, and irradiating the composition layer with active energy rays to develop a developer A method for producing a patterned resin film, comprising: a step of forming a pattern by contacting with a substrate; and a step of heating the composition. Wherein a has a patterned resin film made of a positive photosensitive resin composition according to any one of claims 1-5. A display element comprising a patterned resin film made of the positive photosensitive resin composition according to any one of claims 1 to 5 . It is obtained by patterning on a semiconductor element so that the film thickness after heating the positive photosensitive resin composition according to any one of claims 1 to 5 is 0.1 to 30 µm. A method for manufacturing a semiconductor device. The positive photosensitive resin composition according to any one of claims 1 to 5 is obtained by patterning on a display element substrate so that the film thickness after heating is 0.1 to 30 µm. A method for manufacturing a display element.

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