JP2006126354A - Photosensitive resin composition and method for producing pattern forming resin layer, and semiconductor device and display element containing photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in light blocking effect and capable of patterning without scum, and provide a semiconductor device and a display component. <P>SOLUTION: The photosensitive resin composition contains an alkali-soluble resin (A), a photosensitizing agent (B), and inorganic particles (C) having an average particle diameter of 1-80 nm, wherein the alkali-soluble resin (A) is preferably a polyamide resin. The polyamide resin preferably includes a structure selected from the group consisting of polybenzoxazole precursor structures, polyamide acid structures or polyamide acid ester structures. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a photosensitive resin composition and a method for producing a pattern forming resin layer, and a semiconductor device and a display element including the photosensitive resin composition.

Conventionally, polybenzoxazole resins and polyimide resins having excellent heat resistance and excellent electrical characteristics, mechanical characteristics, and the like have been used for surface protective films and interlayer insulating films of semiconductor elements. In order to simplify the process, a photosensitive resin in which a precursor of polybenzoxazole resin or polyimide resin is combined with a diazoquinone compound as a photosensitive agent is also used (Patent Document 1).
These photosensitive resins change to polybenzoxazole resin or polyimide resin through a thermosetting reaction after pattern formation. The film after the thermosetting reaction has a brown color, and the circuit of the semiconductor element appears to be transmitted. With regard to the transparency of the resin layer, an opaque positive photosensitive resin is recently required from the viewpoint of circuit design confidentiality.

On the other hand, in the field of display elements, liquid crystal display devices, organic EL display devices, and plasma display devices have begun to spread due to demand for personal computers and large-sized televisions. The black matrix used in these display elements is an important material used between colored pixels and used for improving contrast and preventing deterioration of transistor characteristics due to light. In general, a metal-chromium thin film has been used as the black matrix material, but in recent years, a photosensitive resin black matrix obtained by adding a black pigment to a resin has been used. Generally, an acrylic resin is added with a pigment, an initiator, and a cross-linking agent (Patent Document 2), but these acrylic resin-based black matrices contain a large amount of pigment that is not soluble in the developer. The developability is poor and it remains as a scum at the bottom of the pattern or the development time becomes extremely long, which causes a problem in practical use.
Japanese Examined Patent Publication No. 1-46862 Japanese Patent Publication No. 9-184911

However, the prior art described in the above literature has room for improvement in the following points.
First, the resin composition to which no pigment is added has a problem that the circuit of the semiconductor element is seen through after the resin is cured, and the confidentiality cannot be maintained.
Secondly, as seen in the field of display elements, when a black matrix material is used, there is a problem that developability is poor and scum remains at the bottom of the pattern or development time becomes extremely long.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an opaque positive photosensitive resin. Another object of the present invention is to suppress the occurrence of scum and shorten the development time.

（Ｘは２〜４価の有機基、Ｙは２〜６価の有機基である。ａ、ｂはモルパーセントを示し、ａ＋ｂ＝１００で、ａ＝６０〜１００、ｂ＝０〜４０である。Ｒ₁は水酸基又は−Ｏ−Ｒ₃、ｍは０〜２の整数で、同一でも異なっても良い。Ｒ₂は水酸基、カルボキシル基、−Ｏ−Ｒ₃、−ＣＯＯ−Ｒ₃のいずれかであり、同一でも異なっても良い。ｎは０〜４の整数である。Ｒ₃は炭素数１〜１５の有機基である。ここで、Ｒ₁として水酸基がない場合、Ｒ₂は少なくとも１つはカルボキシル基でなければならない。また、Ｒ_２としてカルボキシル基がない場合、Ｒ_１は少なくとも１つは水酸基でなればならない。Ｚは−Ｒ_４−Ｓｉ（Ｒ_６）（Ｒ_７）−Ｏ−Ｓｉ（Ｒ_６）（Ｒ_７）−Ｒ_５−で表され、Ｒ₄、Ｒ₅は２価の有機基であり、Ｒ₆、Ｒ₇は１価の有機基である。）
［５］ 感光剤（Ｂ）がキノンジアジド化合物、又はジヒドロピリジン化合物を含んでなる［１］〜［４］のいずれかに記載の感光性樹脂組成物。
［６］ 無機粒子（Ｃ）が、アルミニウム粒子である［１］〜［５］のいずれかに記載の感光性樹脂組成物。
［７］ ［１］〜［６］のいずれかに記載の感光性樹脂組成物を基板上に塗布して組成物層を形成する工程、該組成物層の所望の部分に活性エネルギー線を照射する工程、活性エネルギー線照射後の該組成物層に現像液を接触させてパターンを形成する工程、該組成物層を加熱する工程を有することを特徴とするパターン形成樹脂層の製造方法。
[8]［１］〜［６］のいずれかに記載の感光性樹脂組成物を含む半導体装置。
[9] [１］〜［６］のいずれかに記載の感光性樹脂組成物を含む表示素子。 Such an object is achieved by the present invention described in the following [1] to [9].
[1] A photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and inorganic particles (C) having an average particle diameter of 1 nm to 80 nm.

[2] The photosensitive resin composition according to [1], wherein the alkali-soluble resin (A) is a polyamide resin.
[3] The photosensitive resin composition according to [2], wherein the polyamide resin comprises a structure selected from the group consisting of a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the alkali-soluble resin (A) has a structure represented by the following general formula (1).

(X is a divalent to tetravalent organic group, and Y is a divalent to hexavalent organic group. A and b are mole percentages, a + b = 100, a = 60-100, b = 0-40. R ₁ is a hydroxyl group or —O—R ₃ , m is an integer of 0 to 2, and may be the same or different, and R ₂ is any one of a hydroxyl group, a carboxyl group, —O—R ₃ , and —COO—R ₃ . N is an integer of 0 to 4. R ₃ is an organic group having 1 to 15 carbon atoms, and when R ₁ has no hydroxyl group, R ₂ is at least 1 One must be a carboxyl group, and if there is no carboxyl group as R _{2 then} at least one R ₁ must be a hydroxyl group Z is —R ₄ —Si (R ₆ ) (R ₇ ) —O _{-Si (R 6) (R 7} ) -R 5 - is represented by, R _4, R ₅ is a divalent organic group, R _6, R ₇ is a monovalent organic group.)
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the photosensitive agent (B) comprises a quinonediazide compound or a dihydropyridine compound.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the inorganic particles (C) are aluminum particles.
[7] A step of coating the photosensitive resin composition according to any one of [1] to [6] on a substrate to form a composition layer, and irradiating a desired portion of the composition layer with active energy rays And a step of forming a pattern by bringing a developer into contact with the composition layer after irradiation with active energy rays, and a step of heating the composition layer.
[8] A semiconductor device comprising the photosensitive resin composition according to any one of [1] to [6].
[9] A display device comprising the photosensitive resin composition according to any one of [1] to [6].

  According to the present invention, it is possible to obtain a photosensitive resin composition that has excellent light shielding properties and that can be patterned without scum, and a semiconductor device and a display element using the same.

  The present invention relates to a photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and inorganic particles (C) having an average particle diameter of 1 nm to 80 nm. Hereinafter, each component of the positive photosensitive resin composition of the present invention will be described in detail. The following is an example, and the present invention is not limited to the following.

The alkali-soluble resin (A) used in the present invention is a resin having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or side chain, and is a cresol type novolak resin, polyhydroxystyrene, or polyamide resin. Of these, polyamide resins are preferred.
The polyamide resin is a resin having a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure and having a hydroxyl group, a carboxyl group, or a sulfonic acid group in the main chain or side chain. 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 there is no hydroxyl group as R _1, R ₂ is at least one 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 the structure represented by the general formula (1) is, for example, a compound selected from diamine having an X structure or bis (aminophenol), 2,4-diaminophenol, and the like, and a tetracarboxylic acid having a Y structure. It is obtained by reacting with a compound selected from anhydride, trimellitic 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 with R ₃ which is an organic group having 1 to 15 carbon atoms, and a hydroxyl group or a carboxyl group may be protected as necessary. Examples of R ₃ include formyl, methyl, ethyl, propyl, isopropyl, tertiary butyl, tertiary butoxycarbonyl, phenyl, benzyl, tetrahydrofuranyl, tetrahydropyranyl 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.

（式中Aは、―CH₂―、―C(CH₃)₂―、―O―、―S―、―SO ₂―、―CO―、―NHCO―、―C(CF₃)₂―、又は単結合である。R₈はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｒ＝０〜２の整数である。また、R₉は水素原子、アルキル基、アルキルエステル基、ハロゲン原子から選ばれた１つを表す。） X in general formula (1)
As, for example, the following formula may be mentioned.

(In the formula, A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, R ₈ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different, and is an integer of r = 0 to 2. R ₉ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom.)

（R_１０はアルキル基、アルキルエステル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｒ＝０〜２の整数である。） Among these, particularly preferred are those selected from the following formulae. These may be used alone or in combination of two or more.

(R ₁₀ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different. R = 0 is an integer of 0 to 2.)

(式中A：―CH₂―、―C(CH₃)₂―、―O―、―S―、―SO ₂―、―CO―、―NHCO―、―C(CF₃)₂―、又は単結合である。R₁₁はアルキル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｒ＝０〜２の整数である。) As Y of General formula (1), the thing of a following formula is mentioned, for example.

(Wherein A: —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or R ₁₁ represents one selected from an alkyl group and a halogen atom, and may be the same or different, and is an integer of r = 0 to 2.)

（R_１２はアルキル基、ハロゲン原子の内から選ばれた１つを表し、それぞれ同じでも異なっていてもよい。ｒ＝０〜２の整数である。） Among these, particularly preferred are those selected from the following formulae. These may be used alone or in combination of two or more.

(R ₁₂ represents one selected from an alkyl group and a halogen atom, and may be the same or different. R = 0 is an integer of 0 to 2.)

  In the present invention, it is desirable to seal the end from the viewpoint of storage stability. 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 functional group for sealing the terminal include those represented by the following formula.

Among these, particularly preferred are those selected from the following formulae. These may be used alone or in combination of two or more.

  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

  As the photosensitizer (B) used in the present invention, a photosensitizer capable of positive patterning can be used, and specifically, a diazoquinone compound or a dihydropyridine compound can be used. The diazoquinone compound is a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, and is a substance known from U.S. Pat. For example, the following are mentioned.

（式中Ｑは、水素原子、式（２）、式（３）のいずれかから選ばれるものである。ここで各化合物のＱのうち、少なくとも１つは式（２）、式（３）である。）

(In the formula, Q is selected from a hydrogen atom, formula (2), and formula (3). Here, at least one of Q of each compound is represented by formula (2) or formula (3). .)

  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. For example, the following may be mentioned. These may be used alone or in combination of two or more.

（式中Ｑは、水素原子、式（２）、式（３）のいずれかから選ばれるものである。ここで各化合物のＱのうち、少なくとも１つは式（２）、式（３）である。）

(In the formula, Q is selected from a hydrogen atom, formula (2), and formula (3). Here, at least one of Q of each compound is represented by formula (2) or formula (3). .)

  Examples of the dihydropyridine compound used in the present invention include 2,6-dimethyl-3,5-diacetyl-4- (2′-nitrophenyl) -1,4-dihydropyridine, 4- (2′-nitrophenyl) -2, 6-dimethyl-3,5-dicarboethoxy-1,4-dihydropyridine, 4- (2 ', 4'-dinitrophenyl) -2,6-dimethyl-3,5-dicarbomethoxy-1,4-dihydropyridine Etc.

  The amount of the photosensitizer (B) used in the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). More preferably, it is 10-30 weight part. If it is less than 1 part by weight, the patterning property of the polyamide resin becomes poor, and if it exceeds 50 parts by weight, the sensitivity is greatly lowered, which is not preferable.

  As the inorganic particles (C) that can be used in the present invention, those that can be added to the photosensitive resin composition and can exhibit the desired light-shielding property can be used. The average particle diameter is preferably 15 nm to 60 nm in terms of light shielding properties and patterning properties. If the particle size is 1 nm or less, aggregation tends to occur, and if it is 80 nm or more, scum is likely to occur during patterning. In addition, since the inorganic particles used in the present invention have a very small particle size, the particle size distribution was determined by visual observation with a transmission electron microscope (TEM) and the X-ray small angle scattering method.

  Examples of the inorganic particles include aluminum, silver, copper, chromium, nickel, titanium, iron, and zinc. Aluminum is preferable from the viewpoint of light shielding properties. The inorganic particles may be in a state where the surface is oxidized by oxygen in the air.

  The amount of the inorganic particles (C) used in the present invention is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (A). More preferably, it is 5-30 weight part. When the amount is 5 parts by weight or less, the light-shielding property is insufficient, and when it is 30 parts by weight or more, patterning is not preferable.

  In the present invention, the alkali-soluble resin (A), the photosensitive agent (B), and the inorganic particles (C) having an average particle diameter of 1 nm to 80 nm are 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.

  As for the dissolution method, in addition to a general mixer, a disperser, and a three roll, a bead mill, an annular bead mill, a beadless disperser, or the like is preferably used to improve dispersibility.

  The method of using the photosensitive resin composition of the present invention is as follows. First, the composition is used as a suitable support, for example, a semiconductor substrate such as a silicon wafer, a ceramic substrate, an aluminum substrate, or a display element such as soda glass or alkali-free glass. Apply to substrate. 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 protective surface film of the semiconductor element. If the film thickness exceeds the upper limit value, it will be difficult to obtain a fine processing pattern. 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. In order to make it transparent using the bleaching property of the photosensitive agent, the entire surface may be exposed before being cured, and then curing may be performed.

  The developing mechanism of this photosensitive resin composition is as follows. In the unexposed area, the diazoquinone compound is hardly soluble in an alkaline aqueous solution due to the effect of inhibiting dissolution in a resin such as polybenzoxazole resin or polyimide resin. In one exposed area, the diazoquinone compound undergoes a chemical change and becomes soluble in an alkaline aqueous solution. By utilizing the difference in solubility between the exposed portion and the unexposed portion to dissolve and remove the exposed portion, a coating film pattern of only the unexposed portion can be created.

  The photosensitive resin composition by this invention can be used for the surface protection film of a semiconductor, an interlayer insulation film, or the interlayer insulation of a multilayer circuit. It is also useful as an interlayer insulating film and black matrix in organic EL elements and liquid crystal display elements.

<< No. 1 >>
[Synthesis of polyamide resin]
Dicarboxylic acid obtained by reacting 4.13 g (0.016 mol) of diphenyl ether-4,4′-dicarboxylic acid with 4.32 g (0.032 mol) of 1-hydroxy-1,2,3-benzotriazole A mixture of acid derivatives (0.016 mol) and 7.33 g (0.020 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were thermometer, stirrer, raw material inlet, Into a four-necked separable flask equipped with a dry nitrogen gas inlet tube, 57.0 g of N-methyl-2-pyrrolidone was added and dissolved. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath. Next, 1.31 g (0.008 mol) of 5-norbornene-2,3-dicarboxylic anhydride dissolved in 7 g of N-methyl-2-pyrrolidone was added, and the mixture was further stirred for 12 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]
Three rolls were used for 10 g of synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone (B-1) having the following structure, 3 g of aluminum particles (C-1) having an average particle size of 20 um and 40 g of γ-butyrolactone. The mixture was dispersed and filtered through a 2 μm fluororesin filter to obtain a translucent photosensitive resin composition.

[Developability evaluation]
This photosensitive resin composition was applied to a 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 4 μm. Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a remaining pattern and a blank pattern with a width of 0.88 to 50 μm are drawn), Nikon g-line stepper NSR-1553G3A The exposure was performed at an exposure amount of 400 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 10 μm pattern had no scum and the pattern was well opened.

[Transmittance evaluation]
The prepared pattern was heated in an oven at 300 ° C./30 minutes, and after curing, a film of about 2 μm was obtained. The film was peeled off by dipping in a 2% hydrofluoric acid aqueous solution, and the transmittance at 400 nm was measured. As a result, the film showed a good light shielding property of 9.5%.

<< No. 2 >>
No. 1 was used instead of 10 g of aluminum particles (C-1) having an average particle diameter of 45 nm used in No. 1, and 10 g of aluminum particles having an average particle diameter of 57 nm were used. Evaluation was performed in the same manner as in 1.
<< No. 3 >>
No. 1 was used instead of 10 g of aluminum particles (C-1) having an average particle diameter of 45 nm used in No. 1, and 10 g of aluminum particles having an average particle diameter of 18 nm were used. Evaluation was performed in the same manner as in 1.
<< No. 4 >>
No. 2,6-dimethyl-3,5-dicarboxymethyl-4- (2′-nitrophenyl) -1,4-dihydropyridine (abbreviated as DHPM) instead of 2 g of the photosensitive diazoquinone (B-1) used in 1 B-2) 3.0 g is used, and otherwise, No. Evaluation was performed in the same manner as in 1.
<< No. 5 >>
[Synthesis of polyamide resin]
Thermometer containing 17.06 g (0.055 mol) of 4,4′-oxydiphthalic anhydride, 8.15 g (0.110 mol) of 2-methyl-2-propanol and 10.9 g (0.138 mol) of pyridine Into a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 150 g of N-methyl-2-pyrrolidone was added and dissolved. 14.9 g (0.110 mol) of 1-hydroxy-1,2,3-benzotriazole was added dropwise to this reaction solution together with 30 g of N-methyl-2-pyrrolidone, and then 22.7 g (0.110 mol) of dicyclohexylcarbodiimide. Was added dropwise together with 50 g of N-methyl-2-pyrrolidone and allowed to react overnight at room temperature. Thereafter, 27.1 g of a dicarboxylic acid derivative (active ester) obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid and 2 mol of 1-hydroxy-1,2,3-benzotriazole with this reaction solution. (0.055 mol) and 44.7 g (0.122 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane are added together with 70 g of N-methyl-2-pyrrolidone at room temperature. Stir for 2 hours. Thereafter, the mixture was reacted at 75 ° C. for 12 hours using an oil bath.
Next, 3.94 g (0.024 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 12 hours to complete the reaction. Others are No. In the same manner as in Example 1, reprecipitation and purification were performed to synthesize the target polyamide resin (A-2).

[Production of resin composition, developability, transmittance evaluation]
10 g of synthesized polyamide resin (A-2), 1.5 g of photosensitive diazoquinone (B-3) having the following structure, and 3 g of aluminum particles are mixed and dispersed in 40 g of γ-butyrolactone using three rolls, and 1 μm fluorine The mixture was filtered with a resin filter to obtain a photosensitive resin composition. Evaluation of developability and transmittance is No. 1 was carried out.

(式中Q_１、Q_２、Q₃の７５％は式（４）で表される官能基、２５％は水素原子である。）

(In the formula, 75% of Q ₁ , Q ₂ and Q ₃ are functional groups represented by formula (4), and 25% are hydrogen atoms.)

(式中Q_１、Q_２、Q₃、Ｑ_４の８７．５％は式（４）で表される官能基、１２．５％は水素原子である。)

(In the formula, 87.5% of Q ₁ , Q ₂ , Q ₃ and Q ₄ is a functional group represented by the formula (4), and 12.5% is a hydrogen atom.)

<< No. 6 >>
After forming an ITO film on the glass substrate by vapor deposition, the ITO film was divided into stripes by an ordinary photolithography method using a photoresist. On top of this, no. The positive photosensitive resin composition obtained in 1 was applied to form a resin layer having a thickness of about 2 μm. Next, using a parallel exposure machine (light source: high-pressure mercury lamp), exposure was performed through a glass mask at an exposure intensity of 25 mW / cm 2 for 10 seconds. Thereafter, the resin layer was immersed and developed in a 2.38% tetramethylammonium hydroxide aqueous solution for 20 seconds to expose portions other than the ITO edge on each stripe, and the ITO edge portion and the ITO removed portion were exposed. Processing was performed so that the resin layer was formed only on the top. Thereafter, the entire resin layer was subjected to post-exposure for 40 seconds at an exposure intensity of 25 mW / cm 2 using the parallel exposure machine used for exposure, and then 1 hour at 230 ° C. in air using a hot air circulation dryer. Heat curing was performed.

After depositing copper phthalocyanine as a hole injection layer and bis-N-ethylcarbazole as a hole transport layer on this substrate under a reduced pressure of 1 × 10 −4 Pa or less, N, N′-diphenyl- N, N′-m-toluyl-4,4′-diamino-1,1′-biphenyl and tris (8-quinolinolate) aluminum were deposited in this order as an electron injection layer. Further, after an aluminum layer is deposited on the second electrode as a second electrode, the aluminum layer is formed into a stripe shape in a direction perpendicular to the stripe of the ITO film by a normal photolithography method using a photoresist. Divided. After the obtained substrate was dried under reduced pressure, the sealing glass plate was bonded using an epoxy adhesive to produce a display element. This display element was treated at 80 ° C. for 200 hours and then applied to both electrodes to drive sequentially. However, the element emitted light without any problem.
<< No. 7 >>
No. 1 was used instead of 3 g of aluminum particles (C-1) having an average particle diameter of 18 nm used in No. 1, and 5 g of aluminum particles having an average particle diameter of 1 μm were used. When the evaluation was performed in the same manner as in No. 1, a 10 μm pattern was opened, but scum was observed.
<< No. 8 >>
No. 1 was used instead of 3 g of aluminum particles (C-1) having an average particle diameter of 18 nm used in No. 1, and 5 g of aluminum particles having an average particle diameter of 5 μm were used. When the evaluation was performed in the same manner as in No. 1, the 10 μm pattern did not open. The 100um pattern opened, but scum was seen.

In Table 1, no. 1-6 are Examples, No. 7 to 8 are comparative examples.

  The present invention provides a photosensitive resin composition having excellent light shielding properties and capable of patterning without scum, and a semiconductor device and a display element using the same.

Claims (9)

  A photosensitive resin composition comprising an alkali-soluble resin (A), a photosensitive agent (B), and inorganic particles (C) having an average particle diameter of 1 nm to 80 nm.   The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) is a polyamide resin.   The photosensitive resin composition according to claim 2, wherein the polyamide resin comprises a structure selected from the group consisting of a polybenzoxazole precursor structure, a polyamic acid structure, or a polyamic acid ester structure. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) has a structure represented by the following general formula (1).

(X is a divalent to tetravalent organic group, and Y is a divalent to hexavalent organic group. A and b are mole percentages, a + b = 100, a = 60-100, b = 0-40. R ₁ is a hydroxyl group or —O—R ₃ , m is an integer of 0 to 2, and may be the same or different, and R ₂ is any one of a hydroxyl group, a carboxyl group, —O—R ₃ , and —COO—R ₃ . N is an integer of 0 to 4. R ₃ is an organic group having 1 to 15 carbon atoms, and when R ₁ has no hydroxyl group, R ₂ is at least 1 One must be a carboxyl group, and if there is no carboxyl group as R _{2 then} at least one R ₁ must be a hydroxyl group Z is —R ₄ —Si (R ₆ ) (R ₇ ) —O _{-Si (R 6) (R 7} ) -R 5 - is represented by, R _4, R ₅ is a divalent organic group, R _6, R ₇ is a monovalent organic group.)   The photosensitive resin composition according to claim 1, wherein the photosensitive agent (B) comprises a quinonediazide compound or a dihydropyridine compound.   The photosensitive resin composition according to any one of claims 1 to 5, wherein the inorganic particles (C) are aluminum particles.   A step of applying the photosensitive resin composition according to any one of claims 1 to 6 on a substrate to form a composition layer, a step of irradiating an active energy ray to a desired portion of the composition layer, an activation energy A method for producing a pattern-forming resin layer, comprising: a step of forming a pattern by bringing a developer into contact with the composition layer after irradiation with radiation; and a step of heating the composition layer.   The semiconductor device containing the photosensitive resin composition in any one of Claims 1-6. The display element containing the photosensitive resin composition in any one of Claims 1-6.