JP4811242B2 - Positive photosensitive resin composition, semiconductor device and display element using the positive photosensitive resin composition - Google Patents

Description

  The present invention relates to a positive photosensitive resin composition, a semiconductor device using the positive photosensitive resin composition, and a 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 protective films and interlayer insulating films of semiconductor elements.
Here, in order to simplify the process when a polybenzoxazole resin or a polyimide resin is used, a positive photosensitive resin composition in which a diazoquinone compound of a photosensitive material is combined with these resins is also used (Patent Document 1). ).
JP-A-1-46862

The prior art described in the above literature has room for improvement in the following points.
The surface protective film and the interlayer insulating film of the conventional semiconductor element have a sufficiently high elastic modulus. Therefore, when a semiconductor package is manufactured with the semiconductor sealing resin, the filler contained in the semiconductor sealing resin has a surface. There has been a problem that the surface of the protective film and the interlayer insulating film is broken through and the reliability of the semiconductor package is lowered.
This invention is made | formed in view of the said situation, The place made into the objective is providing the positive photosensitive resin composition which can implement | achieve comparatively high reliability with a high elasticity modulus.

（式中、ｎは１以上の整数、ｍは０〜２の整数を表す。Ｘ、Ｙは有機基であり、ポリアミド樹脂中に含まれるＹのうち、Ｙ_１が少なくとも一つ以上含まれる。Ｒは水酸基またはアルコキシ基である。）

（式中、Ａｒ_１、Ａｒ_２は芳香族基であり、同一であっても異なっていてもよい。）
本発明では、成分（Ａ）として、芳香族に挟まれた構造のエステルを用いることにより樹脂の結晶性を向上させ、これにより樹脂の弾性率を向上させることができる。
［２］
前記Ｙ_１が下記式で示される［１］記載のポジ型感光性樹脂組成物。

［３］
ポリアミド樹脂中に含まれるＹのうち、前記Ｙ_１が占める割合が５０〜１００％である［１］又は［２］記載のポジ型感光性樹脂組成物。
［４］
ポリアミド樹脂中に含まれるＸのうち、下記式で表されるＸ_１が少なくとも一つ以上含まれる［１］乃至［３］のいずれかに記載のポジ型感光性樹脂組成物。

［５］
ポリアミド樹脂中に含まれるＸのうち、前記Ｘ_１が占める割合が３０〜１００％である［４］記載のポジ型感光性樹脂組成物。
［６］
前記（Ｃ）フェノール性水酸基を有する化合物が、下記式で示される構造である［１］乃至［５］のいずれかに記載のポジ型感光性樹脂組成物。

（式中、Ｒ_１、Ｒ_２はハロゲン原子、アルキル基、アルコキシ基、アルキルエステル基シクロアルキル基、シクロアルコキシ基のいずれかを表す。Ｒ_１、Ｒ_２は同一でも異なっていてもよい。ｍ、ｎは０〜５の整数である。ｐ、ｑは０〜３の整数であり、ｐ＋ｑ≧２である。Ｒ_３は単結合、メチレン基、アルキレン基、酸素原子、カルボニル基、カルボニルエーテル基、硫黄原子、スルホニル基、アゾ基のいずれかを表す。）
［７］
［１］乃至［６］のいずれかに記載のポジ型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し、次いで現像液と接触させてパターンを形成する工程、及び、
該組成物層を加熱する工程、
を含むことを特徴とするパターン形成方法。
［８］
半導体基板と、該半導体基板に設けられた半導体素子と、該半導体素子の上部に設けられた絶縁膜とを備え、
前記絶縁膜は、［１］乃至［６］のいずれかに記載のポジ型感光性樹脂組成物より形成された膜であることを特徴とする半導体装置。
［９］
表示素子用基板と、その表面を覆う絶縁膜と、前記表示素子用基板の上部に設けられた表示素子とを備え、
前記絶縁膜は、［１］乃至［６］のいずれかに記載のポジ型感光性樹脂組成物より形成された膜であることを特徴とする発光装置。
［１０］
半導体チップとその表面を覆う保護膜とを備える半導体装置の製造方法であって、
前記半導体チップ上にポジ型感光性樹脂組成物を塗布して樹脂層を形成する工程、
該樹脂層の所望の部分に活性エネルギー線を照射する工程、及び、
活性エネルギー線照射後の該樹脂層に現像液を接触させ、次いで該樹脂層を加熱することにより前記保護膜を形成する工程、
を含み、
前記ポジ型感光性樹脂組成物が［１］乃至［６］のいずれかに記載のポジ型感光性樹脂組成物であることを特徴とする半導体装置の製造方法。
［１１］
表示素子用基板とその表面を覆う平坦化膜を備える表示素子の製造方法であって、
前記表示素子用基板上にポジ型感光性樹脂組成物を塗布して樹脂層を形成する工程、
該樹脂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樹脂層に現像液を接触させ、次いで該樹脂層を加熱することにより前記平坦化膜を形成する工程、
を含み、
前記ポジ型感光性樹脂組成物が［１］乃至［６］のいずれかに記載のポジ型感光性樹脂組成物であることを特徴とする表示素子の製造方法。 Such an object is achieved by the present invention described in the following [1] to [ 11 ].
[1]
(A) a polyamide resin represented by the general formula (1), and
A positive photosensitive resin composition comprising (B) a photosensitive diazoquinone compound and (C) a compound having a phenolic hydroxyl group .

(In the formula, n represents an integer of 1 or more, and m represents an integer of 0 to 2. X and Y are organic groups, and at least one Y ₁ is included in Y included in the polyamide resin. R is a hydroxyl group or an alkoxy group.

(In the formula, Ar ₁ and Ar ₂ are aromatic groups and may be the same or different.)
In the present invention, the crystallinity of the resin can be improved by using an ester having a structure sandwiched between aromatics as the component (A), whereby the elastic modulus of the resin can be improved.
[2]
The positive photosensitive resin composition according to [1], wherein Y ₁ is represented by the following formula.

[3]
The positive photosensitive resin composition according to [1] or [2], wherein a proportion of Y ₁ contained in the polyamide resin is 50 to 100%.
[4]
The positive photosensitive resin composition according to any one of [1] to [3], wherein at least one X ₁ represented by the following formula is included among X contained in the polyamide resin.

[5]
Of X contained in the polyamide resin, the ratio of the X ₁ is occupied by a 30% to 100% [4] The positive photosensitive resin composition.
[ 6 ]
The positive photosensitive resin composition according to any one of [1] to [5], wherein the compound (C) having a phenolic hydroxyl group has a structure represented by the following formula :

(In the formula, R ₁ and R _{2 each} represent a halogen atom, an alkyl group, an alkoxy group, an alkyl ester group, a cycloalkyl group, or a cycloalkoxy group. R ₁ and R ₂ may be the same or different. , N is an integer of 0 to 5. p and q are integers of 0 to 3 and p + q ≧ 2.R ₃ is a single bond, a methylene group, an alkylene group, an oxygen atom, a carbonyl group, a carbonyl ether group. , Represents a sulfur atom, a sulfonyl group, or an azo group.)
[ 7 ]
A step of applying the positive photosensitive resin composition according to any one of [1] to [ 6 ] onto a substrate to form a composition layer;
Irradiating active energy rays to a desired portion of the composition layer, and then contacting with a developer to form a pattern; and
Heating the composition layer;
A pattern forming method comprising:
[ 8 ]
A semiconductor substrate, a semiconductor element provided on the semiconductor substrate, and an insulating film provided on the semiconductor element;
The semiconductor device, wherein the insulating film is a film formed from the positive photosensitive resin composition according to any one of [1] to [ 6 ].
[ 9 ]
A display element substrate, an insulating film covering the surface, and a display element provided on the display element substrate;
The light-emitting device, wherein the insulating film is a film formed from the positive photosensitive resin composition according to any one of [1] to [ 6 ].
[ 10 ]
A method of manufacturing a semiconductor device comprising a semiconductor chip and a protective film covering the surface thereof,
Applying a positive photosensitive resin composition on the semiconductor chip to form a resin layer;
Irradiating an active energy ray to a desired portion of the resin layer; and
A step of bringing the developer into contact with the resin layer after irradiation with active energy rays, and then forming the protective film by heating the resin layer;
Including
The method of manufacturing a semiconductor device, wherein the positive photosensitive resin composition is the positive photosensitive resin composition according to any one of [1] to [ 6 ].
[ 11 ]
A display element manufacturing method comprising a display element substrate and a planarizing film covering the surface thereof,
Applying a positive photosensitive resin composition onto the display element substrate to form a resin layer;
Irradiating an active energy ray to a desired portion of the resin layer;
A step of bringing the developer solution into contact with the resin layer after irradiation with active energy rays and then heating the resin layer to form the planarizing film;
Including
The positive photosensitive resin composition is the positive photosensitive resin composition according to any one of [1] to [ 6 ], and a method for producing a display element.

  According to the positive photosensitive resin composition of the present invention, a positive photosensitive resin composition capable of realizing a relatively high yield with a high elastic modulus is provided.

The present invention relates to a positive photosensitive resin composition containing (A) a polyamide resin represented by the general formula (1) and (B) a photosensitive diazoquinone compound. The following is an example, and the present invention is not limited to the following. Hereinafter, each component of the positive photosensitive resin composition of the present invention will be described in detail.

The polyamide resin represented by the general formula (1) in the present invention is characterized in that it contains at least one Y ₁ out of Y contained in the polyamide resin. Y ₁ has an ester structure sandwiched between aromatic rings, and the presence of this structure in the polyamide of the present invention improves the crystallinity of the polyamide resin, and a positive photosensitive resin composition using this structure. It is possible to improve the film surface elastic modulus of the surface protective film and the interlayer insulating film manufactured from the product.

Y in the general formula (1) can take various organic groups in addition to Y ₁ . For example, the thing of a following formula is mentioned. These may be used alone or in combination as an organic group other than Y ₁ .

(式中A：−CH₂−、−C(CH₃)₂−、−O−、−S−、−SO ₂−、−CO−、−NHCO−、−C(CF₃)₂−、又は単結合である。R₁₀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の正数である。)

(Wherein A: —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, or R ₁₀ represents one selected from an alkyl group and a halogen atom, and may be the same or different, and is a positive number r = 0 to 2.)

Among these, the following structures are preferable.

（Ｒ_１１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。）

(R ₁₁ represents one selected from an alkyl group and a halogen atom, and each may be the same or different. R = 0 is an integer of 0 to 2.)

In the present invention, among the Y included in the polyamide resin of the general formula (1), the ratio of the Y ₁ is occupied by is preferably 50-100%. More preferably, it is 70 to 100%. When the said ratio is more than a lower limit, there exists a merit that a high elasticity modulus can be maintained.

The polyamide resin represented by the general formula (1) in the present invention preferably contains at least one X ₁ out of X contained in the polyamide resin. X ₁ has a biphenyl structure, and since this structure is present in the polyamide of the present invention, the packing property of the resin is improved, and a surface protective film produced from a positive photosensitive resin composition using the same In addition, the film surface elastic modulus of the interlayer insulating film can be improved.

X in the general formula (1) can take the following organic groups in addition to X ₁ . These may be used alone or in combination as an organic group other than X ₁ .

（式中Aは、−CH₂−、−C(CH₃)₂−、−O−、−S−、−SO ₂−、−CO−、−NHCO−、−C(CF₃)₂−、−COO−、又は単結合である。R₁₂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の正数である。また、R₁₃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。）

(In the formula, A represents —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, -COO-, or a single bond, R ₁₂ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and may be the same or different, each of which is a positive number of r = 0-2. R ₁₃ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom.)

  Among these, preferred are those represented by the following formula.

（R₁₄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良い。ｒ＝０〜２の整数である。）

(R ₁₄ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom;
Each may be the same or different. r is an integer of 0-2. )

In the present invention, among the X contained in the polyamide resin of the general formula (1), the ratio of the X ₁ is occupied by is preferably 30 to 100%. More preferably, it is 50 to 100%. When the said ratio is more than a lower limit, there exists a merit that a high elasticity modulus can be maintained.

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 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 the following.

Among these, the following are particularly preferable. These may be used alone or in combination.

Further, the end-capping method is not particularly limited, and an amine derivative containing an aliphatic group or a cyclic compound group having at least one alkenyl group or alkynyl group as the terminal acid contained in the polyamide resin is used. Can also be capped as an amide. When this polyamide resin is heated at about 250 to 400 ° C., dehydration ring closure occurs, and a heat resistant resin is obtained in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both.

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

式中Ｑは、水素原子、式（５）、式（６）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（５）、式（６）である。

In the formula, Q is selected from a hydrogen atom, formula (5), and formula (6). Here, at least one of Q of each compound is represented by formula (5) or formula (6).

  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. Specific examples thereof include the following formula. These may be used alone or in combination of two or more.

式中Ｑは、水素原子、式（５）、式（６）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（５）、式（６）である。

In the formula, Q is selected from a hydrogen atom, formula (5), and formula (6). Here, at least one of Q of each compound is represented by formula (5) or formula (6).

  A preferred addition amount of the photosensitive diazoquinone compound (B) used in the present invention is 1 to 50 parts by weight with respect to 100 parts by weight of the 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.

Furthermore, in the present invention, it is preferable to use (C) a compound having a phenolic hydroxyl group in combination so that high-sensitivity and patterning can be performed with high resolution without developing residue (scum) during development. As for the compounding quantity of the compound which has a phenolic hydroxyl group, 1-30 weight part is preferable with respect to 100 weight part of resin. The compound having a phenolic hydroxyl group is represented by the general formula (4). Specific examples of the general formula (4) include the following, but are not limited thereto.

Among these, Preferably, it is chosen from the following compounds.

The resin composition and the positive photosensitive resin composition in the present invention may contain additives such as a leveling agent and a silane coupling agent as necessary.
In the present invention, these components 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.

  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 50 μm. When the film thickness is less than the lower limit, it is difficult to sufficiently exert the function as a surface protective film of the semiconductor element, and when the film thickness exceeds the upper limit, it is difficult to obtain a fine processed pattern. 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 as interlayer insulation for multilayer circuits, cover coats for flexible copper-clad plates, solder resist films and liquid crystal alignment films, interlayer insulation films for elements in display elements, etc. It is.

  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.

Hereinafter, the present invention will be described specifically by way of examples.
Example 1
[Synthesis of polyamide resin]
Dicarboxylic acid obtained by reacting 4.58 g (0.016 mol) of diphenyl ester-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 3,3′-diamino-4,4′-dihydroxybiphenyl (4.32 g, 0.020 mol) were thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet tube. And 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]
Soluble in 10 g of synthesized polyamide resin (A-1), 2 g of photosensitive diazoquinone represented by the following formula (B-1), 1 g of a compound having a phenolic hydroxyl group represented by the following formula (C-1), and 70 g of γ-butyrolactone Then, the mixture was filtered through a 0.2 μm fluororesin filter to obtain a positive photosensitive resin composition.

[Developability evaluation]
This positive photosensitive resin composition was applied onto 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 5 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 amount was increased by 200 mJ / cm ² to 10 mJ / cm ² steps. Next, the exposed portion was dissolved and removed by immersing in a 2.38% tetramethylammonium hydroxide aqueous solution for 80 seconds, and then rinsed with pure water for 30 seconds. As a result of observing the pattern, it was confirmed that the exposure was 400 mJ / cm ² and the pattern was well opened up to a pattern of 5 μm.
[Evaluation of the physical properties]
This positive photosensitive resin composition was applied on a 6-inch silicon wafer using a spin coater so as to have a thickness of 5 μm after curing, and then dried on a hot plate at 120 ° C. for 4 minutes, and then using a clean oven. Curing was performed at an oxygen concentration of 1000 ppm or less at 150 ° C./30 minutes + 320 ° C./30 minutes.
Next, as a confirmation example of yield improvement, a reflow resistance test of the obtained cured film was performed. BF-30 (manufactured by Arakawa Chemical) was applied as a flux on the cured film and passed through 260 ° C. reflow twice. Thereafter, the flux was removed by washing with xylene and isopropanol, and the surface of the cured film was observed with an optical microscope, but no cracks or wrinkles were observed.
Next, a tensile test was performed. A cured film having a width of 10 mm was pulled at a rate of 5 mm / min with a tensile measuring machine and measured. The tensile elastic modulus was 6.5 GPa.

Example 2
[Synthesis of polyamide resin]
In the synthesis of the polyamide resin of Example 1, 3,3′-diamino-4,4′-dihydroxybiphenyl was replaced with 4.32 g (0.020 mol) of 3,3′-diamino-4,4′-dihydroxybiphenyl. Except for changing to 4.32 g (0.010 mol) and hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane 3.67 g (0.010 mol), the same procedure as in Example 1 was performed. A polyamide resin was synthesized (A-2).

[Production of resin composition, developability and evaluation of physical properties]
Using the obtained polyamide resin (A-2), a positive photosensitive resin composition was produced and evaluated in the same manner as in Example 1.

Example 3
[Synthesis of polyamide resin]
In the synthesis of the polyamide resin in Example 1, 4.58 g (0.016 mol) of diphenyl ester-4,4′-dicarboxylic acid was replaced with 3.66 g (0.0128) of diphenyl ester-4,4′-dicarboxylic acid. Mol) and diphenyl ether-4,4′-dicarboxylic acid was synthesized in the same manner as in Example 1 except that 0.83 g (0.0032 mol) was used (A-3).

[Production of resin composition, developability and evaluation of physical properties]
Using the obtained polyamide resin (A-3), a positive photosensitive resin composition was produced and evaluated in the same manner as in Example 1.

Example 4
[Synthesis of 4-carboxy-2-methoxyphenyl-4′-carboxybenzoate (hereinafter, CMPCB) and its dichloride]
50 mmol of terephthaloyl chloride (TPC) was placed in an eggplant flask, dehydrated tetrahydrofuran (THF) was added and dissolved, and sealed with a septum cap to give solution A (solute concentration: 15% by weight). Next, 25 mmol of vanillic acid was placed in another eggplant flask, dehydrated THF was added, 100 mmol of pyridine was further added and dissolved, and sealed with a septum cap to obtain a solution B (solute concentration: 15% by weight). Next, B liquid was slowly dripped at the A liquid with the syringe in the ice bath, and it stirred for 24 hours in the thermostat (4 degreeC). Thereafter, THF and pyridine were distilled off with an evaporator to remove excess TPC, and toluene was added to the resulting precipitate. After 1 hour, the supernatant was removed with a Pasteur pipette. This operation was performed again, and excess TPC was almost completely removed, followed by vacuum drying at 75 ° C. for 24 hours. To the obtained product, 120 mL of N, N-dimethylformamide (DMF) was added, dissolved by heating to 100 ° C., cooled to room temperature, and then precipitated into 1.5 L of dilute aqueous NaOH solution (pH 8-9). . By this operation, pyridine hydrochloride was dissolved and removed in water. The obtained precipitate was filtered, vacuum dried at 120 ° C. for 24 hours, dissolved again in DMF, precipitated with dilute aqueous HCl (pH 6-7) for neutralization, filtered, and vacuumed at 120 ° C. for 24 hours. The CMPCB crude product represented by the target formula (7) was obtained by drying (yield 50%).

塩素化は次のようにして行った。ＣＭＰＣＢ（７ｍｍｏｌ）をナスフラスコに取り、塩化チオニル３０ｍＬを加え、更に触媒としてＤＭＦを２滴加えた。還流管を取り付け窒素雰囲気下、１２０℃のオイルバス中で６時間還流し、塩素化を行った。過剰の塩化チオニルを減圧留去してＣＭＰＣＢ二塩素化物の粗生成物を得た。これにトルエン２ｍＬを加え再結晶を行った。この再結晶操作を更に１回行い、６０℃で２４時間真空乾燥して、目的のＣＭＰＣＢ二塩素化物を得た（二塩素化物の収率：８０％）。得られた生成物のＩＲ、^１Ｈ−ＮＭＲスペクトルおよび示差走査熱量曲線を図２〜４にそれぞれ示す。分析の結果、生成物は目的のＣＭＰＣＢ二塩化物であることが確認された。
［ポリベンゾオキサゾール前駆体の重合］
十分に乾燥した攪拌機付密閉反応容器中に３，３’−ジヒドロキシベンジジン４．２５ｍｍｏｌおよび２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン０．７５ｍｍｏｌを入れ、モレキュラーシーブス４Aで脱水済みのＮ−メチル−２−
ピロリドン（ＮＭＰ）２５ｍＬおよびピリジン３５ｍｍｏｌをシリンジにて加えて溶解させた。この溶液にトリメチルシリルクロライド２５ｍｍｏｌをシリンジでゆっくりと滴下し、滴下終了後室温で１時間攪拌してシリル化反応を行った。次にこの溶液に十分に乾燥したリチウムクロライド０．２８ｇ（濃度１．０重量％）を加えて溶解した後、実施例１で合成したＣＭＰＣＢ二塩化物粉末５ｍｍｏｌをゆっくり加え、室温で２４時間重合反応を行なわせて透明で粘稠なポリベンゾオキサゾール前駆体溶液を得た。この溶液を大量の水中に滴下して沈殿させ、洗浄を繰り返し、１００℃で２４時間真空乾燥してポリベンゾオキサゾール前駆体粉末を単離した。
［ポリベンゾオキサゾールの製膜および膜物性評価］
ＮＭＰ中、３０℃で測定したポリベンゾオキサゾール前駆体の固有粘度は１．１１ｄＬ／ｇと高分子量体であった。リチウムクロライドを含まないＮＭＰにこのポリベンゾオキサゾール前駆体粉末を再溶解させ、２０重量%の溶液（ワニス）を得た。これをガラス基板
に塗布し、１２０℃で２時間乾燥して、ポリベンゾオキサゾール前駆体膜を製膜後、窒素中３５０℃で１時間、熱脱水閉環反応を行った。膜中の残留歪を除去するため、基板から
膜を剥がし、更に真空中３５０℃で１時間熱処理して、膜厚１６〜２０μmの強靱なポリ
ベンゾオキサゾール膜を得た。これは如何なる有機溶媒にも不溶であった。得られたポリエステルベンゾオキサゾール膜は１８０°折曲げ試験を行っても破断や亀裂が見られず、可撓性を示した。熱閉環反応の完結は薄膜の赤外線吸収スペクトルから確認した。
膜物性は弾性率５．３４ＧＰａ、破断強度０．１０１ＧＰａ、破断伸び４％、線熱膨張係数２９．７ｐｐｍ／Ｋ、ガラス転移温度２９２℃、誘電率２．８６、５％重量減少温度は窒素中で４６８℃、空気中で４４９℃、吸水率０．３３％であり、キャスト製膜性に加えて、特に目的とする高弾性をほぼ満足した。ポリベンゾオキサゾール膜の赤外線吸収スペクトルを図５に示す。

Chlorination was performed as follows. CMPCB (7 mmol) was placed in an eggplant flask, 30 mL of thionyl chloride was added, and 2 drops of DMF was further added as a catalyst. A reflux tube was attached, and the mixture was refluxed in a 120 ° C. oil bath for 6 hours under a nitrogen atmosphere to perform chlorination. Excess thionyl chloride was distilled off under reduced pressure to obtain a crude product of CMPCB dichlorinated product. To this, 2 mL of toluene was added for recrystallization. This recrystallization operation was further performed once and vacuum-dried at 60 ° C. for 24 hours to obtain a target CMPCB dichlorinated product (dichlorinated product yield: 80%). The IR, ¹ H-NMR spectrum and differential scanning calorimetry curve of the obtained product are shown in FIGS. As a result of analysis, it was confirmed that the product was the target CMPCB dichloride.
[Polymerization of polybenzoxazole precursor]
In a well-dried closed reaction vessel with a stirrer, 4.25 mmol of 3,3′-dihydroxybenzidine and 0.75 mmol of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane were placed, and molecular sieves 4A was used. Dehydrated N-methyl-2-
Pyrrolidone (NMP) 25 mL and pyridine 35 mmol were added and dissolved with a syringe. To this solution, 25 mmol of trimethylsilyl chloride was slowly added dropwise with a syringe, and after completion of the addition, the mixture was stirred at room temperature for 1 hour to carry out a silylation reaction. Next, 0.28 g (concentration: 1.0% by weight) of sufficiently dried lithium chloride was added to this solution and dissolved, and then 5 mmol of CMPCB dichloride powder synthesized in Example 1 was slowly added, followed by polymerization at room temperature for 24 hours. The reaction was carried out to obtain a transparent and viscous polybenzoxazole precursor solution. This solution was dropped into a large amount of water to precipitate, repeated washing, and vacuum drying at 100 ° C. for 24 hours to isolate a polybenzoxazole precursor powder.
[Polybenzoxazole film formation and evaluation of film properties]
The intrinsic viscosity of the polybenzoxazole precursor measured in NMP at 30 ° C. was 1.11 dL / g, which was a high molecular weight product. This polybenzoxazole precursor powder was redissolved in NMP not containing lithium chloride to obtain a 20 wt% solution (varnish). This was applied to a glass substrate, dried at 120 ° C. for 2 hours to form a polybenzoxazole precursor film, and then subjected to a thermal dehydration cyclization reaction at 350 ° C. in nitrogen for 1 hour. In order to remove the residual strain in the film, the film was peeled off from the substrate, and further heat-treated in vacuum at 350 ° C. for 1 hour to obtain a tough polybenzoxazole film having a film thickness of 16 to 20 μm. This was insoluble in any organic solvent. The obtained polyester benzoxazole film showed flexibility even when it was subjected to a 180 ° bending test and showed no breakage or cracks. The completion of the thermal ring closure reaction was confirmed from the infrared absorption spectrum of the thin film.
Film properties are elastic modulus 5.34 GPa, breaking strength 0.101 GPa, breaking elongation 4%, linear thermal expansion coefficient 29.7 ppm / K, glass transition temperature 292 ° C., dielectric constant 2.86, 5% weight loss temperature in nitrogen It was 468 ° C., 449 ° C. in air, and water absorption 0.33%. In addition to the cast film forming property, the target high elasticity was almost satisfied. The infrared absorption spectrum of the polybenzoxazole film is shown in FIG.

<< Comparative Example 1 >>
[Synthesis of polyamide resin]
Dicarboxylic acid obtained by reacting 4.10 g (0.016 mol) of diphenylmethane-4,4′-dicarboxylic acid with 4.32 g (0.032 mol) of 1-hydroxy-1,2,3-benzotriazole Mixture of 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, and drying. Into a four-necked separable flask equipped with a 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-4) was obtained.

[Preparation of resin composition]
10 g of the synthesized polyamide resin (A-4) and 2 g of photosensitive diazoquinone (B-1) having the following structure were dissolved in 50 g of N-methyl-2-pyrrolidone, and then filtered through a 0.2 μm fluororesin filter. Type photosensitive resin composition was obtained.

[Developability and evaluation of physical properties]
Next, evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that wrinkles were generated in the reflow evaluation although a pattern of 7 μm was successfully opened with an exposure amount of 600 mJ / cm ² and a development time of 80 seconds. did it. The tensile elastic modulus was 3.0 GPa.

<< Comparative Example 2 >>
[Production of resin composition, developability and evaluation of physical properties]
In the synthesis of the polyamide resin in Comparative Example 1, 4.10 g (0.016 mol) of diphenylmethane-4,4′-dicarboxylic acid was replaced with 4.13 g (0.016 mol) of diphenyl ether-4,4′-dicarboxylic acid. The synthesis (A-5) of a polyamide resin was carried out in the same manner as in Comparative Example 1 except that the composition was changed to [Production of resin composition, developability and evaluation of physical properties].
Using the obtained polyamide resin (A-5), a positive photosensitive resin composition was prepared and evaluated in the same manner as in Comparative Example 1.

<< Comparative Example 3 >>
Put 5 mmol of 3,3'-dihydroxybenzidine that has been recrystallized and dried in a well-closed sealed reaction vessel with a stirrer, and mix N, N-dimethylacetamide and hexamethylphosphoramide that have been dehydrated with Molecular Sieves 4A 20 mL of a solvent (volume ratio 1: 2) and 3 mL (35 mmol) of pyridine were added by a syringe and dissolved. To this solution, 3 mL (25 mmol) of trimethylsilyl chloride was slowly added dropwise with a syringe, and after completion of the addition, the mixture was stirred at room temperature for 1 hour to carry out a silylation reaction. Next, 0.42 g of sufficiently dried lithium chloride was added to this solution and dissolved, and then 5 mmol of terephthalic acid dichloride was slowly added, followed by polymerization at room temperature for several hours to obtain a transparent and viscous polybenzoxazole precursor. A body solution was obtained. Thereafter, in order to suppress the viscosity of the polymerization solution, the solute concentration was diluted to 2 to 3% by weight with the same mixed solvent used during polymerization, and stirring was continued for another 24 hours at room temperature. The intrinsic viscosity measured at 30 ° C. in the same solvent as the polymerization solvent was 5.6 dL / g. This solution was precipitated in a large amount of water, washed and dried, and then redissolved at 150 ° C. in a polymerization solvent not containing lithium chloride. However, it was hardly dissolved. An oxazole precursor film and a polybenzoxazole film could not be formed. This is because CMPCB was not used as the dicarboxylic acid component, but terephthalic acid was used.

<< Comparative Example 4 >>
5 mmol of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane that has been dried is placed in a well-closed sealed reaction vessel equipped with a stirrer, and N-methyl-2-pyrrolidone that has been dehydrated with molecular sieves 4A 20 mL and pyridine 3 mL (35 mmo)
l) was added with a syringe and dissolved. To this solution was added 3 mL of trimethylsilyl chloride (
25 mmol) was slowly added dropwise with a syringe, and after completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to carry out a silylation reaction. Next, 0.42 g of sufficiently dried lithium chloride was added to this solution and dissolved, then 5 mmol of diterephthalate was slowly added, and a polymerization reaction was carried out at room temperature for several hours to obtain a transparent and viscous polybenzoxazole precursor. A body solution was obtained. Thereafter, in order to suppress the viscosity of the polymerization solution, the solute concentration was diluted to 5% by weight with the same mixed solvent used during polymerization, and stirring was continued for another 24 hours at room temperature. The intrinsic viscosity measured at 30 ° C. in the same solvent as the polymerization solvent was 4.18 dL / g. This solution was precipitated in a large amount of water, washed and dried, and redissolved in a polymerization solvent not containing lithium chloride to obtain a uniform solution of 5% by weight. This was applied to a glass substrate, dried at 80 ° C. for 1 hour, and then subjected to a thermal dehydration cyclization reaction at 360 ° C. for 30 minutes under reduced pressure to obtain a polybenzoxazole film having a thickness of 10 to 20 μm. However, the coefficient of linear thermal expansion of the obtained polybenzoxazole film was as high as 53 ppm / K, and the intended characteristics could not be obtained. This does not use 3,3′-dihydroxybenzidine as a bis (o-aminophenol) component at all, and includes 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane containing a structural unit with low linearity. This is because the in-plane orientation of the polymer chain that occurs during the thermal ring closure reaction is excluded.

The present invention provides a polybenzoxazole resin or a polyimide resin or a copolymer resin thereof capable of realizing a relatively high yield with a high elastic modulus, and a positive photosensitive property excellent in exposure characteristics using them. The resin composition is suitably used for a surface protective film of a semiconductor element, an interlayer insulating film, a surface protective film of a display element, an interlayer insulating film, and the like.

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. The infrared absorption spectrum of CMPCB dichlorinated compound synthesize | combined in Example 4 is shown. ¹ shows the ¹ H-NMR spectrum of the CMPCB dichlorinated compound synthesized in Example 4. The differential scanning calorimetry curve of the CMPCB dichlorinated compound synthesized in Example 4 is shown. The infrared absorption spectrum of the polybenzoxazole thin film produced in Example 4 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 (11)

(A) a polyamide resin represented by the general formula (1), and
A positive photosensitive resin composition comprising (B) a photosensitive diazoquinone compound and (C) a compound having a phenolic hydroxyl group .

(In the formula, n represents an integer of 1 or more, and m represents an integer of 0 to 2. X and Y are organic groups, and at least one Y ₁ is included in Y included in the polyamide resin. R is a hydroxyl group or an alkoxy group.

(In the formula, Ar ₁ and Ar ₂ are aromatic groups and may be the same or different.) The positive photosensitive resin composition according to claim _1, wherein Y ₁ is represented by the following formula.

The positive photosensitive resin composition according to claim 1 or 2, wherein the proportion of Y _{1 in the} Y contained in the polyamide resin is 50 to 100 mol%. The positive photosensitive resin composition according to any one of claims 1 to 3, wherein at least one X ₁ represented by the following formula is contained among X contained in the polyamide resin.

The positive photosensitive resin composition according to claim 4, wherein the proportion of X _{1 in} X contained in the polyamide resin is 30 to 100 mol%. The positive photosensitive resin composition according to any one of claims 1 to 5, wherein the compound (C) having a phenolic hydroxyl group has a structure represented by the following formula.

(In the formula, R ₁ and R _{2 each} represent a halogen atom, an alkyl group, an alkoxy group, an alkyl ester group, a cycloalkyl group, or a cycloalkoxy group. R ₁ and R ₂ may be the same or different. , N is an integer of 0 to 5. p and q are integers of 0 to 3 and p + q ≧ 2.R ₃ is a single bond, a methylene group, an alkylene group, an oxygen atom, a carbonyl group, a carbonyl ether group. , Represents a sulfur atom, a sulfonyl group, or an azo group.) Applying the positive photosensitive resin composition according to any one of claims 1 to 6 on a substrate to form a composition layer;
Irradiating active energy rays to a desired portion of the composition layer, and then contacting with a developer to form a pattern; and
Heating the composition layer;
A pattern forming method comprising: A semiconductor substrate, a semiconductor element provided on the semiconductor substrate, and an insulating film provided on the semiconductor element;
The insulating layer, a semiconductor device which is a film formed from the positive photosensitive resin composition according to any one of claims 1 to 6. A display element substrate, an insulating film covering the surface, and a display element provided on the display element substrate;
The insulating layer, the light emitting device, characterized in that the film formed from the positive photosensitive resin composition according to any one of claims 1 to 6. A method of manufacturing a semiconductor device comprising a semiconductor chip and a protective film covering the surface thereof,
Applying a positive photosensitive resin composition on the semiconductor chip to form a resin layer;
Irradiating an active energy ray to a desired portion of the resin layer; and
A step of bringing the developer into contact with the resin layer after irradiation with active energy rays, and then forming the protective film by heating the resin layer;
Including
The method of manufacturing a semiconductor device, wherein the positive photosensitive resin composition is a positive photosensitive resin composition according to any one of claims 1 to 6. A display element manufacturing method comprising a display element substrate and a planarizing film covering the surface thereof,
Applying a positive photosensitive resin composition onto the display element substrate to form a resin layer;
Irradiating an active energy ray to a desired portion of the resin layer;
A step of bringing the developer solution into contact with the resin layer after irradiation with active energy rays and then heating the resin layer to form the planarizing film;
Including
A method for producing a display element, wherein the positive photosensitive resin composition is the positive photosensitive resin composition according to any one of claims 1 to 6 .

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