JP2013174843A - Photosensitive resin composition, protective film and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition showing excellent adhesiveness of a film obtained from the photosensitive resin composition to a substrate and little changes in the viscosity with lapse of time, and to provide a protective film obtained from the photosensitive resin composition and a semiconductor device having the protective film.SOLUTION: The photosensitive resin composition comprises: a polyamide resin (A) having a benzoxazole precursor structure and/or an imide precursor structure; a photosensitive agent (B) that generates an acid by light; a phenolic resin (C) having a repeating unit expressed by formula (C1) and a repeating unit expressed by formula (C2); and an adhesion assistant (D) containing a reaction product of an acid anhydride or an acid dianhydride with a compound having an amino group and an alkoxysilyl group.

Description

  The present invention relates to a photosensitive resin composition, a protective film, and a semiconductor device.

  In recent years, the importance of polyimide as a heat-resistant insulating material in electronic devices has been increasing. Polyimide has not only excellent heat resistance, but also chemical resistance, radiation resistance, electrical insulation, excellent mechanical properties, etc., so it can be used for flexible printed circuit boards, tape automation bonding substrates, and semiconductors. Currently, it is widely used for various applications such as an element protective film and an interlayer insulating film of an integrated circuit.

  Polyimide polymerizes a solvent-soluble precursor (polyamic acid) by subjecting diamine and tetracarboxylic dianhydride to equimolar polyaddition reaction in a non-catalyst solvent such as N-methyl-2-pyrrolidone, and this varnish is used as a solution. It can be produced relatively easily by cast film formation, drying, and heat dehydration ring closure reaction (imidation reaction). In addition, since the film purity is extremely high, it is suitable for semiconductor applications that hate residual halogens, metal ions, and the like that may cause deterioration of electrical characteristics. Further, it is advantageous in that it is easy to improve the physical properties using various available monomers and easily cope with the increasingly demanded characteristics in recent years.

  Conventionally, the microfabrication of a polyimide film composed of polyimide has been performed by forming a photoresist layer on the polyimide film and etching a portion exposed by development with hydrazine or alkali. However, by using photosensitive polyimide with photosensitive performance imparted to polyimide or its precursor itself, the microfabrication process of the polyimide film is greatly shortened, and the production speed and yield rate of semiconductor elements equipped with the polyimide film are expected to be improved. Is done.

  For this purpose, an alkali development positive photosensitive polyimide in which a diazonaphthoquinone photosensitizer is dispersed in a polyamic acid film as a polyimide precursor has been studied. However, since the carboxyl group in the polyamic acid has a low pKa value of 4 to 5, the solubility of the polyamic acid is too high for the 2.38 wt% tetraammonium hydroxide aqueous solution usually used in the semiconductor manufacturing process. There is a problem that it is not suitable for fine processing.

  In recent years, the demand for fine processing with higher resolution has been increasing year by year. Instead of the photosensitive polyimide precursor unsuitable for alkali development as described above, it has a phenolic hydroxy group having a higher pKa value (about 10). Therefore, a (positive type) photosensitive resin composition in which a polybenzoxazole precursor (polyhydroxyamide) exhibiting moderate alkali solubility, a photosensitive agent, and an adhesion assistant has been used (for example, , See Patent Document 1).

  The polybenzoxazole film obtained by thermal ring closure reaction of polyhydroxyamide, which is a polybenzoxazole precursor, not only has excellent microfabrication properties as described above, but also has heat resistance equivalent to polyimide and low resistance superior to polyimide. Since it has water absorption, it is expected as a substitute for polyimide membrane.

  This polybenzoxazole film is required to have excellent adhesion to various substrates such as a semiconductor element and an integrated circuit in order to reliably exhibit functions such as a protective film (interlayer insulating film).

  Furthermore, the polybenzoxazole film is formed by patterning after supplying the photosensitive resin composition onto the substrate using a coating method such as a spin coating method and drying it. In order to improve the film forming accuracy, it is required that the photosensitive resin composition has little change with time in viscosity.

  Therefore, as the photosensitive resin composition, it is necessary that the film obtained from the photosensitive resin composition is excellent in adhesion to the substrate, and the viscosity of the photosensitive resin composition is less changed with time, Such a photosensitive resin composition is not known at present.

JP 2004-1700611 A

  An object of the present invention is a photosensitive resin composition in which a film obtained from a photosensitive resin composition has excellent adhesion to a substrate and has little change with time in viscosity, a protective film obtained from the photosensitive resin composition, and An object of the present invention is to provide a semiconductor device including such a protective film.

［式（Ｃ１）中、Ｚ^１は芳香族環を少なくとも１つ含む基を表し、水酸基は直接芳香族環に結合するものとする。］

［式（Ｃ２）中、Ｚ^２は芳香族環を少なくとも１つ含む基を表し、Ｒ^１’、Ｒ^２’、Ｒ^３’およびＲ^４’は、それぞれ独立して、水素原子、炭素数１〜２０のフッ素原子を含んでもよい炭化水素基である。］ Such an object is achieved by the present invention described in the following (1) to (8).
(1) a polyamide resin (A) having a benzoxazole precursor structure and / or an imide precursor structure;
A photosensitizer (B) that generates acid by light; and
A phenol resin (C) having a repeating unit represented by the following formula (C1) and a repeating unit represented by the following formula (C2);
A photosensitive resin composition comprising an adhesion assistant (D) containing a reaction product of an acid anhydride or acid dianhydride and a compound having an amino group and an alkoxysilyl group.

[In the formula (C1), Z ¹ represents a group containing at least one aromatic ring, and the hydroxyl group is directly bonded to the aromatic ring. ]

[In formula (C2), Z ² represents a group containing at least one aromatic ring, and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} each independently represent a hydrogen atom or a carbon number of 1 It is a hydrocarbon group which may contain -20 fluorine atoms. ]

［式（Ａ１）中、Ｘ、Ｙは有機基である。Ｒ^１は水酸基、カルボキシル基、−Ｏ−Ｒ^３、−ＣＯＯ−Ｒ^３のいずれかであり、Ｒ^１が複数ある場合は、同一でも異なっていてもよい。Ｒ^２は、水素原子、炭素数１〜１５の有機基である。ｌは０〜８の整数である。また、Ｒ^３は、炭素数１〜１５の有機基である。また、ａは重合度を示し、２〜５００である。］ (2) The photosensitive resin composition according to (1), wherein the polyamide resin (A) has a structure represented by the following general formula (A1).

[In the formula (A1), X and Y are organic groups. R ¹ is any ^one of a hydroxyl group, a carboxyl group, —O—R ³ , and —COO—R ³ , and when there are a plurality of R ^{1 s} , they may be the same or different. R ² is a hydrogen atom or an organic group having 1 to 15 carbon atoms. l is an integer of 0-8. R ³ is an organic group having 1 to 15 carbon atoms. Moreover, a shows a polymerization degree and is 2-500. ]

(3) In the phenol resin (C), the group Z ¹ is a phenylene group or a derivative thereof, and the group Z ² is a phenylene group, a biphenylene group, or a derivative thereof, described in (1) or (2) above Photosensitive resin composition.

  (4) The phenol resin (C) is one obtained by alternately connecting the repeating unit represented by the general formula (C1) and the repeating unit represented by the general formula (C2). The photosensitive resin composition in any one of 3).

  (5) The phenol resin (C) has a content of 5 parts by weight or more and 70 parts by weight or less based on 100 parts by weight of the polyamide resin [A]. The photosensitive resin composition as described in 2.

  (6) The adhesion assistant (D) has a content of 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyamide resin [A]. The photosensitive resin composition as described.

(7) The polyamide resin (A) contained in the photosensitive resin composition according to any one of (1) to (6) above contains a benzoxazole structure and / or an imide structure generated by a ring-closing reaction. Features a protective film.
(8) A semiconductor device comprising the protective film according to (7).

  According to this invention, the film | membrane obtained from the photosensitive resin composition can be made excellent in the adhesiveness with respect to a board | substrate.

  Furthermore, it can be set as the photosensitive resin composition with little change with time of a viscosity. Therefore, using a coating method such as a spin coating method, the film formation accuracy of the film formed from this photosensitive resin composition can be improved. In addition, when the viscosity of the photosensitive resin composition changes with time, when the photosensitive resin composition is supplied onto the substrate using a coating method such as a spin coating method, the viscosity changes depending on the viscosity change. By changing the supply conditions, a film having a uniform film thickness can be formed. However, according to the photosensitive resin composition of the present invention, such a change in the supply conditions in accordance with the viscosity change is omitted. Therefore, workability can be improved.

  Furthermore, a semiconductor device having excellent adhesion and having a film formed with a uniform film thickness as a protective film has excellent reliability.

It is a longitudinal cross-sectional view which shows an example of a semiconductor device.

  Hereinafter, a photosensitive resin composition, a protective film, and a semiconductor device will be described in detail based on preferred embodiments shown in the accompanying drawings.

  First, prior to describing the photosensitive resin composition of the present invention, a semiconductor device provided with a film formed using the photosensitive resin composition as a protective film (chip coat film) will be described.

<Semiconductor device>
FIG. 1 is a longitudinal sectional view showing an example of a semiconductor device. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

  A semiconductor device 10 illustrated in FIG. 1 is a QFP (Quad Flat Package) type semiconductor package, and includes a semiconductor chip (semiconductor element) 20, a die pad 30 that supports the semiconductor chip 20 via an adhesive layer 60, and the semiconductor chip 20. A lead film 40 electrically connected to the semiconductor chip 20, and a mold part 50 for sealing the semiconductor chip 20.

  The die pad 30 is composed of a metal substrate and functions as a support for supporting the semiconductor chip 20.

  The die pad 30 includes, for example, a metal substrate made of various metal materials such as Cu, Fe, Ni, and alloys thereof (for example, Cu-based alloys and iron / nickel-based alloys such as Fe-42Ni), The surface of the metal substrate is plated with silver or Ni—Pd, and the surface of the Ni—Pd plating is provided with a gold plating (gold flash) layer provided to improve the stability of the Pd layer. Are used.

  Moreover, the planar view shape of the die pad 30 usually corresponds to the planar view shape of the semiconductor chip 20 and is, for example, a square such as a square or a rectangle.

A plurality of leads 40 are provided radially on the outer periphery of the die pad 30.
An end portion of the lead 40 opposite to the die pad 30 protrudes (exposes) from the mold portion 50.

  Further, the exposed portion of the lead 40 from the mold portion 50 may be subjected to surface treatment such as gold plating, tin plating, solder plating, or solder coating on the surface thereof. Thereby, when the semiconductor device 10 is connected to the terminals provided on the mother board via the solder, the adhesion between the solder and the leads 40 can be improved.

  Further, such a surface treatment of the lead 40 is not limited to the exposed portion from the mold portion 50, and may be applied to the entire lead 40.

  The lead 40 is made of a conductive material, and for example, the same material as that of the die pad 30 described above can be used.

  The semiconductor chip 20 is fixed (fixed) to the die pad 30 via an adhesive layer 60 formed of a cured product of a resin composition (liquid resin composition).

  The adhesive layer 60 has a function of connecting the die pad 30 and the semiconductor chip 20 and a function of transmitting (dissipating) heat generated when the semiconductor chip 20 is driven to the die pad 30 side.

  The adhesive layer 60 includes, for example, a metal powder such as silver powder, aluminum powder, and nickel powder, or ceramic powder such as silica powder, alumina powder, and titania powder as an filler, an epoxy resin, an acrylic compound, Those composed of a thermosetting resin such as polyimide resin are preferably used.

  The semiconductor chip 20 has an electrode pad 21 on its upper surface, and the electrode pad 21 and the lead 40 are electrically connected by a wire 22. Thereby, the semiconductor chip 20 and each lead 40 are electrically connected.

  Although the material of this wire 22 is not specifically limited, The wire 22 can be comprised by Au wire or Al wire, for example.

  A protective film (chip coat film) 70 is formed on the semiconductor chip 20 so that the electrode pads 21 are exposed.

  This protective film 70 protects the semiconductor chip when it is formed by curing and shrinking the mold part, and protects against thermal shock and abrupt thermal expansion stress of the mold material in the solder reflow process for mounting the semiconductor chip on the substrate. It has a function to perform.

  In the present invention, the protective film 70 is formed using the photosensitive resin composition of the present invention. The constituent materials of the photosensitive resin composition will be described in detail later.

  Furthermore, the die pad 30, each member provided on the upper surface side of the die pad 30, and the portion inside the lead 40 are sealed by the mold part 50. As a result, the outer end portion of the lead 40 protrudes from the mold portion 50.

  This mold part 50 can be comprised with various resin materials, such as an epoxy resin, for example.

<Method for Manufacturing Semiconductor Device>
Such a semiconductor device 10 can be manufactured as follows, for example.

  [1] First, a lead frame including a die pad (support) 30 and a plurality of leads (terminals) 40 is prepared.

  [2] Next, separately from this, the semiconductor chip 20 provided with the protective film 70 patterned so as to expose the electrode pads 21 is prepared.

  Such a protective film 70 can be formed on the semiconductor chip 20 as follows, for example.

  [2-1] First, the photosensitive resin composition of the present invention is prepared as a liquid material (varnish), and this liquid material is supplied using a coating method so as to cover almost the entire top surface of the semiconductor chip 20. .

  Examples of the coating method include a spin coating method using a spinner, a spray coating method using a spray coater, a dipping method, a printing method, a roll coating method, and the like. Can be used in combination.

  Among these, when the spin coating method is used, the photosensitive resin composition of the present invention is preferably used. That is, since the time-dependent change in the viscosity of the photosensitive resin composition is small, the labor for changing the supply conditions for obtaining the protective film 70 having a uniform film thickness in accordance with the change in the viscosity can be saved. The workability at the time can be improved.

  The coating amount is applied so that the final average film thickness of the protective film 70 to be formed is 1 to 20 μm. If the film thickness is less than the lower limit value, the function as the protective surface film of the semiconductor chip 20 may not be sufficiently exhibited. If the film thickness exceeds the upper limit value, it may be difficult to obtain a fine processing pattern. In addition to this, processing takes time and throughput decreases.

  [2-2] Next, by drying the liquid material, a film containing the constituent material contained in the photosensitive resin composition is formed on the upper surface of the semiconductor chip 20.

  In addition, the drying temperature at the time of drying a liquid material becomes like this. Preferably it is about 40-150 degreeC, More preferably, it is set to about 80-130 degreeC. Thereby, it is possible to reliably remove the solvent remaining in the film while effectively preventing the photosensitive agent [B] from being thermally decomposed.

  Moreover, it is preferable that the processing time at the time of drying is about 1 to 30 minutes, and it is more preferable that it is about 2 to 5 minutes.

[2-3] Next, the film formed at a position corresponding to the electrode pad 21 is selectively exposed and exposed using a mask corresponding to the shape of the electrode pad 21, and then etched with an alkaline aqueous solution. Develop with.
Thereby, the film is patterned into a shape in which the electrode pad 21 is exposed.

The light applied to the film formed using the photosensitive resin composition at the time of exposure / sensitivity is not particularly limited, but usually g-line (436 nm) and i-line (365 nm) are used. A line (365 nm) is preferably used. Thereby, the film can be surely patterned into a fine shape. Furthermore, when irradiating i line | wire at room temperature, energy amount is set to about 100-5000mJ / cm < ² >.

  The film formed using the photosensitive resin composition preferably has a light transmittance of 50% or more at i-line (365 nm) when the film thickness is 10 μm, and 70% or more. Is more preferable. Thereby, the said film | membrane can be patterned more reliably in the shape which exposed the electrode pad 21. FIG.

  Further, the aqueous alkali solution (alkaline developer) is not particularly limited. For example, in addition to organic alkali such as tetramethylammonium hydroxide, triethylamine, ethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate Inorganic alkalis such as these can be used, and one or more of these can be used in combination. Especially, the tetramethylammonium hydroxide aqueous solution currently used by the semiconductor process is used suitably. In the tetramethylammonium hydroxide aqueous solution, metal atoms are not included in the molecular structure, and metal atoms do not remain in the formed semiconductor device 10, so there is no possibility that the residual metal will adversely affect electrical characteristics. At this time, the concentration of the tetramethylammonium hydroxide aqueous solution is set to about 0.05 to 10% by weight, preferably about 0.1 to 5% by weight, and more preferably 2.38% by weight. And it develops for 10 seconds-10 minutes at room temperature using this alkaline aqueous solution, and also by rinsing with a pure water, a clear positive pattern can be obtained.

  In some cases, alcohols may be added to the alkaline aqueous solution. Examples of usable alcohols include methanol, ethanol, 1-propanol, 2-propanol and the like.

  [2-4] Next, a polyamide resin contained in the patterned film, that is, a resin having a benzoxazole precursor structure and / or an imide precursor structure is subjected to a ring-closing reaction (curing reaction) to obtain a benzoxazole structure and The protective film 70 is obtained by using a resin having an imide structure.

  In addition, the cyclization reaction of the resin having a benzoxazole precursor structure and / or an imide precursor structure can be smoothly advanced, for example, by heating a patterned film.

  The temperature for heating the film is preferably in the range of 180 to 400 ° C, more preferably in the range of 250 to 350 ° C.

  The heating time is preferably in the range of 1 to 60 minutes, and more preferably in the range of 10 to 30 minutes.

  The atmosphere for heating may be an air atmosphere, but is preferably an inert atmosphere such as nitrogen or a reduced pressure atmosphere. Thereby, a ring-closing reaction can be advanced more reliably.

  The average film thickness of the protective film 70 is preferably about 1 to 20 μm, and more preferably about 5 to 10 μm. Thereby, the function as a protective film mentioned above can be exhibited reliably.

  [3] Next, the constituent material of the adhesive layer 60 before curing is supplied onto the die pad 30 by using a commercially available discharge device such as a die bonder.

  [4] Next, the semiconductor chip 20 is placed on the die pad 30 with the surface on which the protective film 70 is provided on the die pad 30 so that the constituent material of the adhesive layer 60 before curing is interposed, and heated. To do. Thereby, the constituent material of the adhesive layer 60 before curing is cured, and the adhesive layer 60 composed of the cured product is formed. As a result, the semiconductor chip 20 is bonded onto the die pad (support) 30 via the adhesive layer 60.

  [5] Next, the conductive wire 22 is formed between the electrode pad 21 exposed from the protective film 70 and the lead 40 by wire bonding. Thereby, the electrode pad 21 and the lead 40 are electrically connected.

[6] Next, the mold part 50 is formed by, for example, transfer molding.
Thereafter, a resin-fixed tie bar is punched out from the lead frame, and a trim and foam process is performed to manufacture the semiconductor device 10.

<Protective film 70>
In such a semiconductor device 10, the protective film 70 has a higher elastic modulus, a lower water absorption rate, and a finer film for the purpose of exhibiting the function as the protective film 70 described above. What has the more excellent translucency is calculated | required so that it can pattern into a shape.

  In recent years, for the purpose of obtaining a product excellent in such properties, this protective film (chip coat film) contains polybenzoxazole formed using a photosensitive resin composition containing a polybenzoxazole precursor. Various studies have been made on the film to be used.

  Specifically, as described in the background art, a photosensitive resin composition is proposed that includes a polybenzoxazole precursor (polyhydroxyamide), a photosensitive agent, and an adhesion aid. Has been.

  In such a photosensitive resin composition, the elastic modulus, water absorption, and transmissivity of the film formed using the photosensitive resin composition are improved, and the adhesion to the semiconductor chip (substrate) 20 is further improved. Can be improved.

  However, according to the study of the present inventors, the viscosity of the photosensitive resin composition changes with time depending on the type of the adhesion assistant by making the photosensitive resin composition to contain the adhesion assistant. Has come to understand.

  When the viscosity changes with time as described above, the photosensitive resin composition is applied to the upper surface of the semiconductor chip 20 as in the spin coating method as described in the steps [2-1] and [2-2]. After supplying using the method, the film forming accuracy is reduced by drying. In addition, when supplying the photosensitive resin composition to the upper surface of the semiconductor chip 20 using a coating method, a film having a uniform film thickness can be formed by changing supply conditions according to the change in viscosity. However, in this case, it is necessary to set the supply conditions according to the magnitude of the viscosity change, which causes a problem that the workability is complicated.

  As a result of intensive studies on the problem, the present inventor has obtained a photosensitive resin composition having a formula (C1) described below in addition to a polybenzoxazole precursor (polyhydroxyamide), a photosensitizer and an adhesion aid. ) Change of the viscosity of the photosensitive resin composition over time by including a phenol resin having a repeating unit (structural unit) represented by formula (C2) and a repeating unit (structural unit) represented by formula (C2). It was found that can be suppressed or prevented accurately.

  That is, a polyamide resin (A) having a benzoxazole precursor structure and / or an imide precursor structure, a photosensitive agent (B) that generates an acid by light, a repeating unit represented by the following formula (C1), and the following formula Adhesion aid (D) comprising a reaction product of a phenol resin (C) having a repeating unit represented by (C2), an acid anhydride or an acid dianhydride, and a compound having an amino group and an alkoxysilyl group The present invention has been completed by finding that the above-mentioned problems can be solved by using a composition containing.

［式（Ｃ１）中、Ｚ^１は芳香族環を少なくとも１つ含む基を表し、水酸基は直接芳香族環に結合するものとする。］

[In the formula (C1), Z ¹ represents a group containing at least one aromatic ring, and the hydroxyl group is directly bonded to the aromatic ring. ]

［式（Ｃ２）中、Ｚ^２は芳香族環を少なくとも１つ含む基を表し、Ｒ^１’、Ｒ^２’、Ｒ^３’およびＲ^４’は、それぞれ独立して、水素原子、炭素数１〜２０のフッ素原子を含んでもよい炭化水素基である。］
以下、感光性樹脂組成物に含まれる各構成材料について、順次、説明する。

[In formula (C2), Z ² represents a group containing at least one aromatic ring, and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} each independently represent a hydrogen atom or a carbon number of 1 It is a hydrocarbon group which may contain -20 fluorine atoms. ]
Hereinafter, each constituent material contained in the photosensitive resin composition will be sequentially described.

[Polyamide resin (A)]
In the present invention, the polyamide resin (A) is an alkali-soluble resin having a benzoxazole precursor structure and / or an imide precursor structure, and is included as a main material of the photosensitive resin composition.

  In addition, in addition to the benzoxazole precursor structure and the imide precursor structure, the polyamide resin has a cyclization reaction on a part of the benzoxazole structure and imide precursor structure generated by a part of the benzoxazole precursor structure. It may have an imide structure produced by the above, and may further have an amic acid ester structure.

  The benzoxazole precursor structure refers to a structure represented by the following formula (A2), the imide precursor structure refers to a structure represented by the following formula (A3), and the benzoxazole structure refers to the following: The structure represented by the formula (A4) is referred to, the imide structure refers to the structure represented by the following formula (A5), and the amido ester structure refers to the structure represented by the following formula (A6). In the following formulas (A2) to (A6), D and R ′ each represents an organic group.

  The weight average molecular weight (Mw) of the polyamide resin (A) is not particularly limited, but is preferably 5000 or more and 20000 or less, and more preferably 6000 or more and 18000 or less. If the weight average molecular weight is less than the above lower limit value, film loss may increase during exposure and exposure after exposure. If the weight average molecular weight exceeds the above upper limit value, depending on the etching conditions, the exposed portion to be etched There is a risk of increased residue after exposure.

  Further, the polyamide resin (A) may have a resin terminal sealed after the polymerization reaction in order to complete the synthesis reaction more stably.

  For example, when the resin terminal is an amine residue, it can be sealed with a carboxylic acid anhydride or an active ester. By sealing the amine terminal, it is possible to improve the preservability of the photosensitive resin composition.

  In addition, when sealed with a carboxylic acid anhydride, the terminal structure may form an amide bond or an imide bond, but the terminal structure may be any bond.

  As the carboxylic acid anhydride, an aliphatic or cyclic compound having an alkenyl group or an alkynyl group is preferable.

  Examples of the active ester include compounds obtained by reacting an aliphatic or cyclic carboxylic acid compound having an alkenyl group or an alkynyl group with 1-hydroxy-1,2,3-benzotriazole.

  Furthermore, when the resin terminal is a carboxylic acid, it can be sealed with an amine-containing compound or the like. The amine-containing compound is preferably an unsaturated aniline compound or a nitrogen-containing heterocyclic compound. Thereby, the adhesion of the protective film 70 to the upper surface of the semiconductor chip 20 can be improved.

  Among these polyamide resins (A), those having a structure represented by the following general formula (A1) are particularly preferable.

［式（Ａ１）中、Ｘ、Ｙは有機基である。Ｒ^１は水酸基、カルボキシル基、−Ｏ−Ｒ^３、−ＣＯＯ−Ｒ^３のいずれかであり、Ｒ^１が複数ある場合は、同一でも異なっていてもよい。Ｒ^２は、水素原子、炭素数１〜１５の有機基である。ｌは０〜８の整数である。また、Ｒ^３は、炭素数１〜１５の有機基である。また、ａは重合度を示し、２〜５００である。］

[In the formula (A1), X and Y are organic groups. R ¹ is any ^one of a hydroxyl group, a carboxyl group, —O—R ³ , and —COO—R ³ , and when there are a plurality of R ^{1 s} , they may be the same or different. R ² is a hydrogen atom or an organic group having 1 to 15 carbon atoms. l is an integer of 0-8. R ³ is an organic group having 1 to 15 carbon atoms. Moreover, a shows a polymerization degree and is 2-500. ]

  In the protective film 70 obtained by heating and curing the photosensitive resin composition by using the polyamide resin (A) having the structure represented by the general formula (A1), an imide ring and / or Or an oxazole ring is formed. As a result, the heat resistance of the protective film (cured film) 70 can be improved, and as a result, the reliability of the semiconductor device 10 including the protective film 70 is improved.

  The polyamide resin having the structure represented by the general formula (A1) is, for example, a compound selected from a bis (aminophenol) derivative containing a group X, a diaminophenol derivative and the like, and a tetracarboxylic acid anhydride containing a group Y. , A polyamide resin obtained by reacting with a compound selected from trimellitic anhydride, dicarboxylic acid or dicarboxylic acid dichloride, dicarboxylic acid derivative, hydroxydicarboxylic acid, hydroxydicarboxylic acid derivative, and the like.

  When a dicarboxylic acid derivative containing a group Y is used, it is preferable to use an active ester type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance. Thereby, the reaction yield of the amide resin having the structure represented by the general formula (A1) can be increased.

In the general formula (A1), the group R ² is not particularly limited as long as it is independently a hydrogen atom or an organic group having 1 to 15 carbon atoms. Group, ethyl group, propyl group, isopropyl group, tertiary butyl group, tertiary butoxycarbonyl group, phenyl group, benzyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. By appropriately selecting these, the solubility of the polyamide resin (A) in the alkaline aqueous solution can be adjusted.

In general formula (A1) in the group Y substituents ^{R 1} as mentioned is ^{-O-R 3,} R 3 of ^{-COO-R 3} also, those having the same function as that of the ^{R 2, R 2} The thing similar to is mentioned as an example.

  When the polyamide resin having the structure represented by the general formula (A1) is heated, dehydration cyclization occurs, and as a result, the cured resin in the form of polyimide resin, polybenzoxazole resin, or copolymerization of both is present in the protective film 70. It is formed. Thereby, the protective film 70 has excellent heat resistance.

  In the polyamide resin having the structure represented by the general formula (A1), the group X is an organic group and is not particularly limited. For example, an aromatic compound such as a benzene ring or a naphthalene ring, bisphenol Heterocyclic compounds such as pyrrole, pyrrole, furan, etc., more specifically, preferably those represented by the following formula (A7), and one or more of these are combined. Can be used.

［式（Ａ７）中、＊はＮＨ基に結合することを示す。Ｅは、−ＣＨ_２−、ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、−ＮＨＣＯ−、―Ｃ（ＣＦ_３）_２―または単結合である。Ｒ⁴は、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つを示し、Ｒ⁴が複数ある場合は、それぞれ同じでも異なっていてもよい。Ｒ⁵は、アルキル基、アルコキシ基、アシルオキシ基、シクロアルキル基のいずれかである。Ｒ⁵が複数ある場合は、同じでも異なっていてもよい。Ｒ⁶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つを示す。ｙは０〜２の整数、ｚは０〜３の整数である。Ｒ^７〜Ｒ^１０は、有機基である。］

[In formula (A7), * indicates binding to an NH group. E represents —CH ₂ —, CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF _{3 2} ) or a single bond. R ⁴ represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and when there are a plurality of R ^{4 s} , they may be the same or different. R ⁵ is any one of an alkyl group, an alkoxy group, an acyloxy group, and a cycloalkyl group. When there are a plurality of R ^{5 s} , they may be the same or different. R ⁶ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. y is an integer of 0 to 2, and z is an integer of 0 to 3. R ^{7 to} R ¹⁰ are organic groups. ]

  Among the groups X represented by the formulas (7-1) to (7-7) represented by the formula (A7), the group X represented by the following formula (A8) is preferable. Thereby, the protective film 70 containing the polyimide resin, polybenzoxazole resin, or the copolymer of both obtained after the spin-drying | dehydration ring closure of a polyamide resin (A) is equipped with the outstanding mechanical characteristic.

［式（Ａ８）中、＊はＮＨ基に、※は−ＯＲ^２基に結合することを示す。Ｆ、Ｇは、それぞれ、−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、 −ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。aは、それぞれ独立して、０〜３の整数であり、Ｒ¹¹は、アルキル基、 アルコキシル基、アシルオキシ基、シクロアルキル基の内から選ばれた１つを表す。 Ｒ^１1が複数ある場合は、それぞれ同じでも異なっていてもよい。］

[In the formula (A8), * represents an NH group, and * represents an —OR ² group. F and G are respectively —CH ₂ —, —CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, -C _{(CF 3) 2} -, or a single bond. a is each independently an integer of 0 to 3, and R ¹¹ represents one selected from an alkyl group, an alkoxyl group, an acyloxy group, and a cycloalkyl group. When there are a plurality of R ^{11 's} , they may be the same or different. ]

  In the polyamide resin having the structure represented by the general formula (A1), the group Y is an organic group and is not particularly limited. For example, aromatic compounds such as a benzene ring and a naphthalene ring, bisphenols And heterocyclic compounds such as pyrroles, pyridines and furans, siloxane compounds, and the like. More specifically, those represented by the following formula (A9) are preferable, and one of these is exemplified. Or it can be used in combination of two or more.

［式（Ａ９）中、＊はＣ＝Ｏ基に結合することを示す。J、Ｋは、それぞれ独立して、−ＣＨ_２−、ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＣＯ−、 −ＮＨＣＯ−、−Ｃ（ＣＦ_３）_２−、または単結合である。Ｒ^１2 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、Ｒ^１2が複数ある場合は、それぞれ同じでも異なっていてもよい。また、Ｒ^１3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。ｂは０〜４の整数である。Ｒ^１4 〜Ｒ^１7は有機基である。］

[In formula (A9), * indicates binding to a C═O group. J and K are each independently —CH ₂ —, CH (CH ₃ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO. _{-, - C (CF 3)} 2 -, or a single bond. R ¹² represents one selected from an alkyl group, an alkyl ester group, and a halogen atom, and when there are a plurality of R ^{12 s} , they may be the same or different. R ¹³ represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group, and a halogen atom. b is an integer of 0-4. R ^{14 to} R ¹⁷ are organic groups. ]

  The amount of the hydroxystyrene / styrene copolymer is preferably 1 part by weight or more and 99 parts by weight or less of the hydroxystyrene / styrene copolymer when the total amount of the polyamide resin (A) is 100 parts by weight. More preferably, it is 5 parts by weight or more and 80 parts by weight or less. By setting it as the said range, the film | membrane containing a polyamide resin (A) can be made highly sensitive, and the protective film (cured film) 70 can be excellent in a mechanical characteristic.

  Moreover, since the polyamide resin (A) having such a configuration exhibits excellent solubility in a solvent described later, it is supplied onto the semiconductor chip 20 using a liquid material containing the polyamide resin (A). By drying, a film containing the polyamide resin (A) can be formed.

  The polyamide resin (A) may be any polymer as long as it has a benzoxazole precursor structure and / or an imide precursor structure, and the benzoxazole precursor structure or the imide precursor structure is a single polymer. Alternatively, it may be a copolymer composed of a benzoxazole precursor structure and an imide precursor structure, or an amide structure and / or an imide different from the benzoxazole precursor structure and the imide precursor structure. It may be a copolymer containing a structure.

[Photosensitive agent (B)]
The photosensitive agent (B) is a compound that generates an acid by light.

  When a photosensitive agent is contained in the photosensitive resin composition, the film obtained by drying the photosensitive resin composition is selectively irradiated with light, thereby being positioned in the light irradiation region. The solubility of the film in the alkaline aqueous solution can be improved as compared with the solubility of the film located in the non-irradiated region of the film in the alkaline aqueous solution. Therefore, the film located in the light irradiation region can be selectively removed (etched) by etching using this alkaline aqueous solution. That is, the photosensitive resin composition can be a positive photosensitive resin composition.

  Examples of the photosensitizer (B) include onium salts such as diphenyliodonium salt and triphenylsulfonium salt, 2-nitrobenzyl esters, N-iminosulfonates, arylsulfonic acid esters, and heterocyclic rings having halogen such as chlorine. Formula compounds and photosensitive diazoquinone compounds can be mentioned, and one or more of them can be used in combination.

  Of these compounds, photosensitive diazoquinone compounds are preferred. Since such a compound is most excellent in sensitivity and resolution in the wavelength range of actinic radiation mainly used for exposure, the protective film 70 can be formed with excellent patterning accuracy.

  Examples of the photosensitive diazoquinone compound include esters of a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, Examples thereof include ester compounds represented by the formulas (B10) to (B14). These may be used alone or in combination of two or more.

［式（Ｂ１０）中、Ｒ_２０は、水素原子、またはメチル基である。］

[In the formula (B10), R ₂₀ represents a hydrogen atom or a methyl group. ]

［式（Ｂ１２）中、Ｒ_２１は、それぞれ独立して、水素原子、またはメチル基である。］

[In formula (B12), each R ₂₁ independently represents a hydrogen atom or a methyl group. ]

［式（Ｂ１３）中、Ｒ_２２は、それぞれ独立して、水素原子、またはメチル基である。］

[In formula (B13), each R ₂₂ independently represents a hydrogen atom or a methyl group. ]

［式（Ｂ１４）中、Ｒ_２３は、それぞれ独立して、水素原子、またはメチル基である。］

[In Formula (B14), each R ₂₃ independently represents a hydrogen atom or a methyl group. ]

  In the formulas (B10) to (B14), Q is selected from a hydrogen atom or any one of the following formulas (B15) and (B16), and at least one of Q of each compound is It is the following formula (B15) or the following formula (B16).

  Among these, the photosensitizers of the above formulas (B12), (B13), and (B14) are particularly preferable. Thereby, the sensitivity and resolution of the photosensitive resin composition can be further improved.

  Although content of a photosensitive agent (B) is not specifically limited, It is preferable that it is 1 to 50 weight part with respect to 100 weight part of said polyamide resin [A], 10 to 40 weight part is preferable. It is more preferable that Thereby, the difference of the solubility with respect to aqueous alkali solution of a light irradiation area | region (exposure part) and a light non-irradiation area | region (non-exposure part) can be expressed reliably.

[Phenolic resin (C)]
The phenol resin (C) has a repeating unit represented by the following formula (C1) and a repeating unit represented by the following formula (C2).

［式（Ｃ１）中、Ｚ^１は芳香族環を少なくとも１つ含む基を表し、水酸基は直接芳香族環に結合するものとする。］

[In the formula (C1), Z ¹ represents a group containing at least one aromatic ring, and the hydroxyl group is directly bonded to the aromatic ring. ]

［式（Ｃ２）中、Ｚ^２は芳香族環を少なくとも１つ含む基を表し、Ｒ^１’、Ｒ^２’、Ｒ^３’およびＲ^４’は、それぞれ独立して、水素原子、炭素数１〜２０のフッ素原子を含んでもよい炭化水素基である。］

[In formula (C2), Z ² represents a group containing at least one aromatic ring, and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} each independently represent a hydrogen atom or a carbon number of 1 It is a hydrocarbon group which may contain -20 fluorine atoms. ]

  By including the phenol resin (C) having such a configuration in the photosensitive resin composition, the phenol resin (C) functions as an auxiliary agent for the adhesion assistant (D) described later. Therefore, the bonding strength (adhesiveness) between the film obtained by exposing and developing the photosensitive resin composition and the semiconductor chip 20, and the bonding between the protective film 70 obtained by curing the film and the semiconductor chip 20 Strength can be improved more reliably.

  Furthermore, in the photosensitive resin composition of the present invention, by using a reaction product of an acid anhydride or an acid dianhydride and a compound having an amino group and an alkoxysilyl group as an adhesion assistant (D) described later, Although the time-dependent change in the viscosity of the photosensitive resin composition is accurately suppressed, the adhesion aid (D) can be obtained by adopting a configuration in which the phenol resin (C) is included in the photosensitive resin composition. The content in the photosensitive resin composition can be set low. Therefore, also from this viewpoint, the change with time of the viscosity of the photosensitive resin composition can be more accurately suppressed or prevented.

The group Z ¹ , group Z ² , group R ^{1 ′} to group R in the general formula (C1) and the general formula (C2) so that the function of the phenol resin (C) is more suitably exhibited. ^{4 ′} is appropriately selected.

The group Z ¹ is not particularly limited as long as it contains at least one aromatic ring, but one having a linear structure is preferably used and has 1 to 3 aromatic rings. It is preferable that it has one aromatic ring. Thereby, the solubility with respect to the aqueous alkali solution of a photosensitive resin composition, adhesiveness, and transparency can be made excellent.

In addition, the aromatic ring contained in the group Z ¹ may be either substituted or unsubstituted, and when provided with a substituent, examples of the substituent include a hydroxyl group, an alkoxyl group, a carbon number of 1 to The hydrocarbon group which may contain 20 fluorine atoms, a halogen atom, an ester group, a carbonyl group, an amino group, an aromatic group, etc. are mentioned. When a plurality of substituents are provided, these substituents may be the same or different.

  Specifically, examples of the structure of such a group include those represented by the following formula (C3).

The group Z ¹ is preferably composed of an aromatic hydrocarbon ring composed of a carbon atom and a hydrogen atom. Thereby, the linearity of the main skeleton can be improved as compared with those including a flex bond such as an ether bond and a sulfonyl bond. Therefore, it is possible to improve the solubility, adhesion and transparency of the photosensitive resin composition in an aqueous alkali solution.

Considering these facts, as the group Z ¹ , a phenylene group or a derivative thereof is a particularly preferable structure. Thereby, it can be set as the phenol resin (C) excellent in adhesiveness especially.
The hydroxyl for coupling to Z ¹ is directly attached to the aromatic ring contained in Z ^1.

Further, the group Z ² is not particularly limited as long as it contains at least one aromatic ring. However, like the group Z ¹ , those having a linear structure are preferably used, and 1 to 4 It preferably has an aromatic ring, and more preferably has one or two aromatic rings. Thereby, it can be made especially excellent in adhesiveness, maintaining the solubility with respect to the aqueous alkali solution of the photosensitive resin composition.

The aromatic ring contained in the group Z ² may be either substituted or unsubstituted. When the substituent is provided, examples of the substituent include an alkoxyl group and a C 1-20 carbon atom. Examples thereof include a hydrocarbon group that may contain a fluorine atom, a halogen atom, an ester group, a carbonyl group, an amino group, and an aromatic group. When a plurality of substituents are provided, these substituents may be the same or different. However, a substituent in which a hydroxyl group is directly connected to an aromatic ring is excluded.

  Specifically, examples of the structure of such a group include those represented by the formula (C3).

The base Z ² is preferably composed aromatic hydrocarbon ring composed of carbon atoms and hydrogen atoms. Thereby, the linearity of the main skeleton can be improved as compared with those including a flex bond such as an ether bond and a sulfonyl bond. Therefore, among the solubility and adhesiveness of the phenol resin (C), it is possible to particularly improve the adhesiveness.

  Further, when two or more aromatic rings are included, the plurality of aromatic rings may have any structure of a linked polycyclic system and a condensed polycyclic system, but have a linked polycyclic structure. It is preferable. Thereby, a phenol resin (C) can be made excellent in both solubility and adhesiveness.

Considering these facts, the group Z ² is particularly preferably a phenylene group, a biphenylene group or a derivative thereof. Thereby, it can be set as the phenol resin (C) excellent in adhesiveness especially.

Further, the groups R ^{1 ′} to R ^{4 ′} are each independently a hydrocarbon group that may contain a hydrogen atom or a fluorine atom having 1 to 20 carbon atoms. Among these, the groups R ^{1 ′} to R ^{4 ′} are preferably a hydrogen atom or a methyl group. Thereby, a phenol resin (C) can be made excellent in both solubility and adhesiveness.

  From the above, it is particularly preferable that the phenol resin (C) has a structure represented by the following general formulas (C4) to (C6).

［式（Ｃ４）〜（Ｃ６）中、ｎは０以上の整数を表す。］

[In formulas (C4) to (C6), n represents an integer of 0 or more. ]

  In the phenol resin (C), the repeating unit represented by the general formula (C1) and the repeating unit represented by the general formula (C2) may be linked irregularly (randomly). These repeating units (C1) and (C2) are preferably linked alternately. Thereby, the function as a phenol resin (C) can be exhibited uniformly now in a phenol resin (C).

  The addition amount of the phenol resin (C) is preferably 5 parts by weight or more and 70 parts by weight or less, and more preferably 10 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the polyamide resin [A]. preferable. By making the addition amount in the above range, the bonding strength between the protective film 70 and the semiconductor chip 20 can be improved more reliably, and the change with time in the viscosity of the photosensitive resin composition can be more accurately suppressed or prevented. can do.

[Adhesion aid (D)]
The adhesion assistant (D) contains a reaction product (amino group-containing silane coupling agent) of an acid anhydride or acid dianhydride and a compound having an amino group and an alkoxysilyl group.

  When the adhesion assistant (D) having such a configuration is contained in the photosensitive resin composition, the bonding strength (adhesion) between the film obtained by drying the photosensitive resin composition and the semiconductor chip 20 is further increased. The bond strength between the protective film 70 and the semiconductor chip 20 obtained by curing the film can be improved.

  Usually, in order to improve the adhesion between the protective film 70 and the semiconductor chip 20, it is possible to use 3-glycidoxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, or the like. However, when such a compound is used as an adhesion aid, there is a problem that the viscosity of the photosensitive resin composition changes with time. On the other hand, in the present invention, a reaction product of an acid anhydride or an acid dianhydride and a compound having an amino group and an alkoxysilyl group is included with the photosensitive resin composition as an adhesion aid (D). Therefore, the change with time of the viscosity of the photosensitive resin composition can be accurately suppressed.

  Examples of such adhesion assistant (D) include organosilicon compounds represented by the following general formulas (D1) and (D2).

［式（Ｄ１）中、Ｒ_１５、Ｒ_１６は、互いに独立して、１価の有機基を表す。Ｒ_１７、Ｒ_１８は、互いに独立して、２価の有機基を表す。ｌは０〜２の整数を表す。］

[In formula (D1), R ₁₅ and R ₁₆ each independently represent a monovalent organic group. R ₁₇ and R ₁₈ each independently represent a divalent organic group. l represents an integer of 0-2. ]

［式（Ｄ２）中、Ｒ_１９は４価の有機基を表す。Ｒ_２０は２価の有機基を表す。Ｒ_２１、Ｒ_２２は、互いに独立して、１価の有機基を表す。ｌは０〜２の整数を表す。］

[In the formula (D2), R ₁₉ represents a tetravalent organic group. R ₂₀ represents a divalent organic group. R ₂₁ and R ₂₂ each independently represent a monovalent organic group. l represents an integer of 0-2. ]

  In addition, the organosilicon compound represented by the general formulas (D1) and (D2) includes an acid anhydride or an acid dianhydride, and a compound having an amino group and an alkoxysilyl group in an organic solvent at 20 to 100 ° C. For 30 minutes to 10 hours.

  The acid anhydride is not particularly limited. For example, maleic anhydride, dimethyl maleic anhydride, succinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhymic anhydride, hexahydrophthalic anhydride , Tetrahydrophthalic acid, phthalic anhydride and the like, and one or more of them can be used in combination.

  Further, the acid dianhydride is not particularly limited, and examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,3 ′, 4,4 ′. -Benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3 , 6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1, 4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydro Naphthalene-1,2,5,6 Tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene -1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene- 1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyltetracarboxylic dianhydride, 3,3 " , 4,4 "-p-terphenyltetracarboxylic dianhydride 2,2 ", 3,3" -p-terphenyltetracarboxylic dianhydride, 2,3,3 ", 4" -p-terphenyltetracarboxylic dianhydride, 2,2-bis (2 , 3-Dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-di Carboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3 4-dicarboki Ciphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11 -Tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6, 7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4 , 5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4'-hexafluoroisopropylidenediphthalic dianhydride, etc. It can be used alone or in combination.

  The compound having an amino group and an alkoxysilyl group (a silicon compound having an amino group) is not particularly limited. For example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldi Ethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropylethyldi Ethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropyldiethylethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyl Reethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 4-aminobutyldimethylmethoxysilane and the like can be mentioned, and one or more of these can be used in combination. .

  In addition, as a compound shown as the said general formula (D1), the compound like following formula (D11)-(D14) is mentioned, for example.

［式（Ｄ１１）〜（Ｄ１４）中、Ｒ_１８は、下記式（Ｄ１５）〜（Ｄ１７）のうちのいずれかである。］

[In the formulas (D11) to (D14), R ₁₈ is any one of the following formulas (D15) to (D17). ]

  Furthermore, examples of the compound represented by the general formula (D2) include compounds represented by the following formulas (D21) to (D24).

［式（Ｄ２１）〜（Ｄ２４）中、Ｒ_１９は、下記式（Ｄ２５）〜（Ｄ２８）のうちのいずれかである。］

[In the formulas (D21) to (D24), R ₁₉ is any one of the following formulas (D25) to (D28). ]

  The addition amount of the adhesion assistant (D) is preferably 0.1 to 20 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin [A]. By setting the addition amount in the above range, the mechanical strength of the protective film 70 formed on the semiconductor chip 20 can be improved, and the stress generated in the protective film 70 can be relaxed. Moreover, the time-dependent change of the viscosity of the photosensitive resin composition resulting from inclusion of the adhesion assistant (D) can be more accurately suppressed.

[Solution Accelerator (E)]
The photosensitive resin composition may contain a dissolution accelerator (E) in addition to the constituent materials (A) to (D).

  The dissolution accelerator (E) has a function of improving solubility in an aqueous alkali solution (developer) in a light irradiation region (exposed portion) of a film formed using the photosensitive resin composition. Accordingly, it is possible to accurately suppress or prevent the occurrence of scum when the film is etched and patterned.

  Examples of such a dissolution accelerator include compounds having a phenolic hydroxyl group, and specific examples include those represented by the following formulas (E1) to (E7). Species or a combination of two or more can be used.

  Among these compounds having a phenolic hydroxyl group, those selected from the formula (E8) are preferable. Thereby, especially the sensitivity with respect to light of the film | membrane obtained by drying the photosensitive resin composition can be improved.

  Although content of a solubility promoter (E) is not specifically limited, It is preferable that it is 1-30 weight part with respect to 100 weight part of polyamide resin [A], and it is more preferable that it is 1-20 weight part. . As a result, the generation of scum during etching of the film obtained by drying the photosensitive resin composition can be more effectively suppressed, and the sensitivity is further improved by promoting the solubility of the exposed portion. To do.

[solvent]
In addition, the solvent contained in the photosensitive resin composition, that is, the solvent used when dissolving the constituent materials [A] to [E] is not particularly limited. For example, N-methyl-2-pyrrolidone ( NMP), γ-butyrolactone, N, N′-dimethylacetamide (DMAc), 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, lactic acid Ethyl, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3 Include methoxy propionate, it can be used as a single solvent or a mixed solvent of these. Among these, N-methyl-2-pyrrolidone (NMP) or N, N′-dimethylacetamide (DMAc) is preferably used from the viewpoint of ease of handling such as solubility in PHA, toxicity, and flammability.

  In the photosensitive resin composition, additives such as an antioxidant, a filler, a surfactant, a photopolymerization initiator, a crosslinking agent, a terminal blocking agent, and a sensitizer are added as necessary. Also good.

  The photosensitive resin composition, protective film, and semiconductor device of the present invention have been described above, but the present invention is not limited to these.

  For example, the semiconductor device of the present invention has been described as applied to a QFP type semiconductor package. However, the present invention is not limited to such a case. For example, the DIP (Dual In-line Package) type, SOP (Small Out-line) is used. The present invention can also be applied to package packages, LF-CSP (Lead Frame Chip Scale Package) types, and BGA (Ball Grid Array) type semiconductor packages.

  Furthermore, although the semiconductor device of this invention demonstrated the case where one semiconductor chip (semiconductor element) was fixed on the die pad (support body), it is not limited to this, A several semiconductor element is on a support body It may be fixed.

  In addition to the die pad, the support for supporting the semiconductor chip may be a heat radiating member such as a heat sink or a heat spreader.

  Furthermore, the configuration of each part of the semiconductor device of the present invention can be replaced with any component that can exhibit the same function, or can be added with any configuration.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.

1. Preparation of photosensitive resin composition << Example 1 >>
[Synthesis of Polyamide Resin (A-1)]
Dicarboxylic acid obtained by reacting 21.43 g (0.083 mol) of diphenyl ether-4,4′-dicarboxylic acid with 22.43 g (0.166 mol) of 1-hydroxy-1,2,3-benzotriazole 40.87 g (0.083 mol) of the derivative mixture and 36.62 g (0.100 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane were added to a thermometer, a stirrer, Into a four-necked separable flask equipped with a raw material inlet and a dry nitrogen gas inlet tube, 296.96 g of N-methyl-2-pyrrolidone was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath.

  Next, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added. The reaction was terminated by stirring for 3 hours.

  After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 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. In addition, the weight average molecular weight of the obtained compound was 13,040.

[Synthesis of Photosensitive Agent (Q-1)]
11.00 g (0.026 mol) of phenol of the formula (C-1), 18.78 g (0.070 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 170 g of acetone are thermometers, The mixture was stirred and dissolved in a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube.

  Next, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. Next, after filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), and then the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum. A photosensitizer represented by the structure of formula (Q-1) was obtained.

[Production of (Positive) Photosensitive Resin Composition]
8.5 g of the polyamide resin (A-1) synthesized above, 1.5 g of Millex XLC-4L (Mitsui Chemical Co., Ltd.) as the phenol resin, 1 g of the photosensitive agent (Q-1) synthesized above, and the formula (D 1) 0.1 g of a silicon compound (adhesion aid) represented by the structure is dissolved in 16 g of γ-butyrolactone, and then filtered through a 0.2 μm fluororesin filter. The photosensitive resin composition of Example 1 Got.

<< Example 2 >>
In the production of the photosensitive resin composition of Example 1, Example 2 was performed in the same manner as in Example 1 except that Millex XLC-3L (manufactured by Mitsui Chemicals, Inc.) was used as the phenol resin instead of Milex XLC-4L. A photosensitive resin composition was prepared.

Example 3
In the production of the photosensitive resin composition of Example 1, the same as in Example 1 except that MEH-7800SS (manufactured by Meiwa Kasei Co., Ltd.) was used as the phenol resin instead of Milex XLC-4L. A photosensitive resin composition was prepared.

Example 4
In preparation of the photosensitive resin composition of Example 1, the addition amount of the polyamide resin (A-1) was changed from 8.5 g to 6.5 g, and the addition amount of Millex XLC-4L was changed from 1.5 g to 3.5 g. In the same manner as in Example 1, a photosensitive resin composition of Example 4 was prepared.

Example 5
In the production of the photosensitive resin composition of Example 1, the addition amount of the polyamide resin (A-1) was changed from 8.5 g to 4.5 g, and the addition amount of Millex XLC-4L was changed from 1.5 g to 5.5 g. In the same manner as in Example 1, the photosensitive resin composition of Example 5 was prepared.

Example 6
In the production of the photosensitive resin composition of Example 1, the photosensitive resin composition of Example 6 was the same as Example 1 except that the addition amount of the photosensitive agent (Q-1) was changed from 1 g to 1.2 g. Was made.

Example 7
[Synthesis of Polyamide Resin (A-2)]
Dicarboxylic acid obtained by reacting 21.43 g (0.083 mol) of diphenyl ether-4,4′-dicarboxylic acid with 22.43 g (0.166 mol) of 1-hydroxy-1,2,3-benzotriazole 40.87 g (0.083 mol) of a mixture of derivatives, 21.98 g (0.060 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane and 4,4′-methylenebis ( 2-aminophenol) 9.21 g (0.040 mol) was placed in a four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet and a dry nitrogen gas inlet tube, and N-methyl-2- Pyrrolidone 296.96 g was added and dissolved. Then, it was made to react at 75 degreeC for 15 hours using the oil bath.

  Next, 6.98 g (0.0425 mol) of 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride dissolved in 34.88 g of N-methyl-2-pyrrolidone was added. The reaction was terminated by stirring for 3 hours.

  After filtering the reaction mixture, the reaction mixture was poured into a solution of water / isopropanol = 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. In addition, the weight average molecular weight of the obtained compound was 21,170.

[Preparation of photosensitive resin composition]
The photosensitive resin of Example 7 was the same as Example 1 except that the polyamide resin (A-2) was used instead of the polyamide resin (A-1) in the production of the photosensitive resin composition of Example 1. A composition was prepared.

Example 8
The photosensitive resin of Example 8 was the same as Example 4 except that the polyamide resin (A-2) was used instead of the polyamide resin (A-1) in the production of the photosensitive resin composition of Example 4. A composition was prepared.

Example 9
[Synthesis of Polyamide Resin (A-3)]
4-nose Separa equipped with 30.0 g (0.082 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane equipped with a thermometer, stirrer, raw material inlet and dry nitrogen gas inlet tube The solution was placed in a bull flask and dissolved by adding 400 ml of acetone.

  Next, 12.4 g (0.18 mol) of para-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise over 30 minutes while cooling so that the temperature was less than 20 ° C. to obtain a mixture. After the addition, the temperature of the mixture was heated to 40 ° C. and stirred for 2 hours, and then 30.0 g (0.218 mol) of potassium carbonate was gradually added and further stirred for 2 hours. Heating was stopped and the mixture was further stirred at room temperature for 18 hours. Thereafter, while vigorously stirring the mixture, an aqueous sodium hydroxide solution was gradually added. After the addition, the mixture was heated to 55 ° C. and further stirred for 30 minutes. After completion of the stirring, the mixture was cooled to room temperature, 37% by weight hydrochloric acid aqueous solution and 500 ml of water were added, and the pH of the solution was adjusted to be in the range of 6.0 to 7.0. Next, the obtained precipitate was filtered off, the filtrate was washed with water and dried at 60 to 70 ° C., and bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2 A solid of bis (4-hydroxyphenyl) propane was obtained.

  To 51.0 g of the obtained solid, 316 g of acetone and 158 g of methanol were added and heated to 50 ° C. to be completely dissolved. Thereto, 300 mL of pure water at 50 ° C. was added over 30 minutes and heated to 65 ° C. Thereafter, the crystals which have been slowly cooled to room temperature are filtered, and the crystals are purified by drying at 70 ° C. to obtain bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis. (4-Hydroxyphenyl) propane was obtained.

  20 g of the bis-N, N ′-(para-nitrobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was placed in a 1 L flask and 1.0 g of 5% palladium-carbon and acetic acid. 180.4 g of ethyl was added to make a suspension. Hydrogen gas was purged there, and the mixture was shaken for 35 minutes while being heated to 50 to 55 ° C. to carry out a reduction reaction. After completion of the reaction, it was cooled to 35 ° C. and the suspension was purged with nitrogen. After removing the catalyst by filtration, the filtrate was subjected to an evaporator to evaporate the solvent. The obtained product was dried at 90 ° C. to obtain bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane.

  14.27 g (0.024 mol) of bis-N, N ′-(para-aminobenzoyl) hexafluoro-2,2-bis (4-hydroxyphenyl) propane obtained above was added to a thermometer, a stirrer, and a raw material inlet. And put into a four-necked separable flask equipped with a dry nitrogen gas inlet tube, 40 g of γ-butyrolactone was added and dissolved, and the mixture was cooled to 15 ° C. with stirring. Thereto, 6.86 parts by weight (0.022 mol) of 4,4′-oxydiphthalic anhydride and 12.0 parts by weight of γ-butyrolactone were added and stirred at 20 ° C. for 1.5 hours. Thereafter, the mixture was heated to 50 ° C. and stirred for 3 hours. Then, 5.27 g (0.044 mol) of N, N-dimethylformamide dimethylacetal and 10.0 g of γ-butyrolactone were added, and the mixture was further stirred at 50 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature to obtain the target polyamide resin (A-3). In addition, the weight average molecular weight of the obtained compound was 13200.

[Preparation of photosensitive resin composition]
The photosensitive resin of Example 9 is the same as Example 1 except that the polyamide resin (A-3) is used instead of the polyamide resin (A-1) in the production of the photosensitive resin composition of Example 1. A composition was prepared.

Example 10
The photosensitive resin of Example 10 was the same as Example 4 except that the polyamide resin (A-3) was used instead of the polyamide resin (A-1) in the production of the photosensitive resin composition of Example 4. A composition was prepared.

Example 11
[Synthesis of Photosensitizer (Q-2)]
A thermometer containing 11.02 g (0.026 mol) of phenol represented by the formula (C-2), 18.78 g (0.070 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 170 g of acetone. The mixture was stirred and dissolved in a four-necked separable flask equipped with a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube.

  Next, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35 ° C. After reacting for 3 hours at room temperature, 1.05 g (0.017 mol) of acetic acid was added, and the reaction was further continued for 30 minutes. After filtering the reaction mixture, the filtrate was put into a mixed solution of water / acetic acid (990 ml / 10 ml), the precipitate was collected by filtration, washed thoroughly with water, and dried under vacuum to obtain the formula (Q-2 ) Was obtained.

[Preparation of photosensitive resin composition]
In the production of the photosensitive resin composition of Example 1, the photosensitive resin of Example 11 was used in the same manner as in Example 1 except that the photosensitive agent (Q-2) was used instead of the photosensitive agent (Q-1). A composition was prepared.

Example 12
In the production of the photosensitive resin composition of Example 1, the photosensitive resin of Example 12 was the same as Example 1 except that the addition amount of the silicon compound (D-1) was changed from 0.1 g to 0.05 g. A composition was prepared.

Example 13
In the production of the photosensitive resin composition of Example 1, the photosensitive resin of Example 13 was the same as Example 1 except that the addition amount of the silicon compound (D-1) was changed from 0.1 g to 0.3 g. A composition was prepared.

≪Comparative example 1≫
After 10 g of polyamide resin (A-1), 1 g of photosensitizer (Q-1) and 0.1 g of silicon compound represented by the structure of formula (D-1) are dissolved in 16 g of γ-butyrolactone, 0.2 μm It filtered with the filter made from a fluororesin, and the photosensitive resin composition of the comparative example 1 was obtained.

«Comparative example 2»
10 g of polyamide resin (A-1), 1 g of photosensitizer (Q-1), 0.1 g of silicon compound represented by the structure of formula (D-1), and silicon compound 0 represented by the structure of formula (D-2) .05 g was dissolved in 16 g of γ-butyrolactone and then filtered through a 0.2 μm fluororesin filter to obtain a photosensitive resin composition.

«Comparative Example 3»
In the production of the photosensitive resin composition of Comparative Example 2, the photosensitive resin of Comparative Example 3 was the same as Comparative Example 2 except that the addition amount of the silicon compound (D-2) was changed from 0.05 g to 0.1 g. A composition was prepared.

<< Comparative Example 4 >>
In the production of the photosensitive resin composition of Comparative Example 2, the photosensitive resin of Comparative Example 4 was the same as Comparative Example 2 except that the addition amount of the silicon compound (D-2) was changed from 0.05 g to 0.3 g. A composition was prepared.

<< Comparative Example 5 >>
In the production of the photosensitive resin composition of Example 1, a comparison was made in the same manner as in Example 1 except that the silicon compound represented by the structure of the formula (D-3) was used instead of the silicon compound (D-1). The photosensitive resin composition of Example 5 was prepared.

<< Comparative Example 6 >>
In the production of the photosensitive resin composition of Comparative Example 1, the photosensitive resin of Comparative Example 6 was the same as Comparative Example 1 except that the polyamide resin (A-2) was used instead of the polyamide resin (A-1). A composition was prepared.

<< Comparative Example 7 >>
The photosensitive resin of Comparative Example 7 was prepared in the same manner as Comparative Example 1 except that the polyamide resin (A-3) was used instead of the polyamide resin (A-1) in the production of the photosensitive resin composition of Comparative Example 1. A composition was prepared.

«Comparative Example 8»
The photosensitive resin of Comparative Example 8 was prepared in the same manner as Comparative Example 1 except that the photosensitive agent (Q-2) was used instead of the photosensitive agent (Q-1) in the production of the photosensitive resin composition of Comparative Example 1. A composition was prepared.

  Table 1 shows the structures of X and Y and the terminal structure of the formula (A1) of the polyamide resin [A] synthesized.

［式（Ａ１）中、Ｘ、Ｙは有機基である。Ｒ^１は水酸基、カルボキシル基、−Ｏ−Ｒ^３、−ＣＯＯ−Ｒ^３のいずれかであり、Ｒ^１が複数ある場合は、同一でも異なっていてもよい。Ｒ^２は、水素原子、炭素数１〜１５の有機基である。ｌは０〜８の整数である。また、Ｒ^３は、炭素数１〜１５の有機基である。また、ａは重合度を示し、２〜５００である。］

[In the formula (A1), X and Y are organic groups. R ¹ is any ^one of a hydroxyl group, a carboxyl group, —O—R ³ , and —COO—R ³ , and when there are a plurality of R ^{1 s} , they may be the same or different. R ² is a hydrogen atom or an organic group having 1 to 15 carbon atoms. l is an integer of 0-8. R ³ is an organic group having 1 to 15 carbon atoms. Moreover, a shows a polymerization degree and is 2-500. ]

2. Evaluation The following evaluation was performed about the photosensitive resin composition obtained by each Example and the comparative example. The evaluation items are shown together with the contents. The obtained results are shown in Table 1.

2-1. i-Line Sensitivity and Resolution The photosensitive resin composition obtained in each Example and Comparative Example was applied on a silicon wafer using a spin coater, and then pre-baked at 120 ° C. for 2 minutes on a hot plate to obtain a film thickness. A coating film of about 9 μm was obtained.

Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 1: a left pattern and a blank pattern having a width of 0.88 to 50 μm are drawn) is passed through a Nikon i-line stepper NSR-4425i. The exposure amount was increased by 50 mJ / cm ² to 10 mJ / cm ² steps.

  Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, adjusting the development time so that the difference between the film thickness after pre-baking and the film thickness after development is 1.5 μm, paddle twice. The exposed portion was dissolved and removed by developing, and then rinsed with pure water for 20 seconds.

  The value of the minimum exposure amount at which a 100 μm square via hole pattern was formed was evaluated as sensitivity.

2-2. Evaluation of Storage Stability First, the viscosity (T1) of each of the photosensitive resin compositions of Examples and Comparative Examples was measured with an E-type viscometer (TV-22 type, manufactured by Toki Sangyo Co., Ltd.).

Next, these photosensitive resin compositions were each allowed to stand at room temperature, and after 7 days, the viscosity (T2) was measured in the same manner as described above, and ((T2) − (T1) / (T1)) × The viscosity increase rate was calculated from 100 (%).
And the obtained viscosity increase rate was evaluated according to the following evaluation criteria.

<Evaluation criteria>
A: Viscosity increase rate is less than 2.5% B: Viscosity increase rate is 2.5% or more, less than 5.0% X: Viscosity increase rate is 5.0 or more

2-3. Evaluation of adhesion after development The photosensitive resin composition obtained in each Example and Comparative Example was applied on a silicon wafer using a spin coater, and then pre-baked at 120 ° C. for 2 minutes on a hot plate to form a film. A film having a thickness of about 9 μm was obtained.

Through this coating film, a mask made by Toppan Printing Co., Ltd. (test chart No. 2: 100 square patterns of 5 μm are drawn), using Nikon's i-line stepper NSR-4425i, Exposure was performed with an exposure amount obtained by adding 100 mJ / cm ² to the minimum exposure amount.

  Next, using a 2.38% tetramethylammonium hydroxide aqueous solution as a developer, adjusting the development time so that the difference between the film thickness after pre-baking and the film thickness after development is 1.5 μm, paddle twice. The exposed portion was dissolved and removed by developing, and then rinsed with pure water for 20 seconds.

  And the adhesiveness after image development was evaluated according to the following evaluation criteria by counting the number of peeled 5 μm square patterns.

<Evaluation criteria>
◎: Number of peeling 5 or less ○: Number of peeling 6 or more, 10 or less ×: Number of peeling 11 or more

2-4. Adhesion evaluation after humidity treatment The photosensitive resin composition obtained in each Example and Comparative Example was applied on a silicon wafer using a spin coater, and then pre-baked at 120 ° C for 2 minutes on a hot plate, A coating film having a thickness of about 9 μm was obtained.

  Next, heat curing was performed at 150 ° C./30 minutes + 320 ° C./30 minutes at an oxygen concentration of 1,000 ppm or less using a clean oven to obtain a cured film.

  On this cured film, 100 squares in total of 10 rows of 1 × 1 (mm) size squares were created with a cutter knife in accordance with JIS K5400.

  This sample was subjected to a pressure cooker test; continuously treated for 24 hours under conditions of 125 ° C., 100%, and 0.2 MPa, and then evaluated according to the following evaluation criteria according to JIS D0202.

<Evaluation criteria>
◎: Number of peeling 5 or less ○: Number of peeling 6 or more, 10 or less ×: Number of peeling 11 or more

  As shown in Table 2, the photosensitive resin compositions obtained in Examples 1 to 13 are superior in sensitivity to i-line compared to the photosensitive resin compositions obtained in Comparative Examples 1 to 8. I understand that. Furthermore, it was confirmed that the rate of increase in viscosity was also reduced and the base adhesion after development and after curing was good.

DESCRIPTION OF SYMBOLS 10 Semiconductor device 20 Semiconductor chip 21 Electrode pad 22 Conductive wire 30 Die pad 40 Lead 50 Mold part 60 Adhesive layer 70 Protective film

Claims (8)

A polyamide resin (A) having a benzoxazole precursor structure and / or an imide precursor structure;
A photosensitizer (B) that generates acid by light; and
A phenol resin (C) having a repeating unit represented by the following formula (C1) and a repeating unit represented by the following formula (C2);
A photosensitive resin composition comprising an adhesion assistant (D) containing a reaction product of an acid anhydride or acid dianhydride and a compound having an amino group and an alkoxysilyl group.

[In the formula (C1), Z ¹ represents a group containing at least one aromatic ring, and the hydroxyl group is directly bonded to the aromatic ring. ]

[In formula (C2), Z ² represents a group containing at least one aromatic ring, and R ^{1 ′} , R ^{2 ′} , R ^{3 ′} and R ^{4 ′} each independently represent a hydrogen atom or a carbon number of 1 It is a hydrocarbon group which may contain -20 fluorine atoms. ] The photosensitive resin composition according to claim 1, wherein the polyamide resin (A) has a structure represented by the following general formula (A1).

[In the formula (A1), X and Y are organic groups. R ¹ is any ^one of a hydroxyl group, a carboxyl group, —O—R ³ , and —COO—R ³ , and when there are a plurality of R ^{1 s} , they may be the same or different. R ² is a hydrogen atom or an organic group having 1 to 15 carbon atoms. l is an integer of 0-8. R ³ is an organic group having 1 to 15 carbon atoms. Moreover, a shows a polymerization degree and is 2-500. ] 3. The photosensitive resin composition according to claim 1, wherein in the phenol resin (C), the group Z ¹ is a phenylene group or a derivative thereof, and the group Z ² is a phenylene group, a biphenylene group, or a derivative thereof. .   The phenol resin (C) is one in which the repeating unit represented by the general formula (C1) and the repeating unit represented by the general formula (C2) are alternately connected. The photosensitive resin composition as described.   The photosensitive resin according to claim 1, wherein the content of the phenol resin (C) is 5 parts by weight or more and 70 parts by weight or less with respect to 100 parts by weight of the polyamide resin [A]. Composition.   The photosensitive resin composition according to claim 1, wherein the content of the adhesion assistant (D) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyamide resin [A]. object.   A protective film comprising a benzoxazole structure and / or an imide structure produced by a ring-closing reaction of the polyamide resin (A) contained in the photosensitive resin composition according to any one of claims 1 to 6.   A semiconductor device comprising the protective film according to claim 7.

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