JP2013088518A - Photosensitive resin composition, method for manufacturing cured relief pattern, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which has excellent solubility in an alkali aqueous solution and imparts a cured film having small variation in residual stress and excellent chemical resistance.SOLUTION: A photosensitive resin composition includes (a) a resin having a phenolic hydroxyl group, (b) a compound reactive to the phenolic hydroxyl group of the resin (a), (c) a photosensitive compound, and (d) a crosslinking agent. The hydrogen of the phenolic hydroxyl group of the resin having a phenolic hydroxyl group can be substituted with another group at a modification ratio of hydroxyl group within a specified range.

Description

  The present invention relates to a photosensitive resin composition that can be used for, for example, a surface protective film (buffer coat film) and an interlayer insulating film (passivation film) of a semiconductor element. More specifically, the present invention relates to a photosensitive resin composition that provides a cured product that is excellent in resolution as a permanent film resist and that is excellent in electrical characteristics and mechanical characteristics.

  Conventionally, polyimide-based resins having excellent heat resistance, mechanical properties, and the like have been widely used for surface protective films, interlayer insulating films, and the like used in semiconductor devices of electronic devices. Various photosensitive polyimide resins and photosensitive polybenzoxazole resins that have been imparted with photosensitivity have been proposed in order to improve film formation accuracy through high integration of semiconductor elements. For example, a photosensitive polyimide resin in which a photocrosslinking group is introduced into a polyimide precursor by ionic bonding (see Patent Document 1) or a photosensitive polyimide resin in which a photocrosslinking group is introduced into a polyimide precursor by an ester bond (see Patent Document 2) ) Have been proposed. Furthermore, a composition comprising a polybenzoxazole precursor and a quinonediazide compound (see Patent Document 3) has been proposed as an alkali development type photosensitive resin. However, since these compositions require a ring-closing step by heating at a high temperature of 300 ° C. or higher for imidization, there is a drawback in that the semiconductor device is damaged.

  For this reason, in recent years, a permanent film made of a resin that does not require ring closure at a high temperature has attracted attention. These have a function as a permanent film such as a surface protective film for a semiconductor by curing at a temperature of 300 ° C. or less, preferably 250 ° C. or less. Further, there is a type that can be developed with an inexpensive alkaline aqueous solution. preferable. Specifically, a composition obtained by adding a photoacid generator and a crosslinking agent (negative type) or a naphthoquinonediazide compound (positive type) to a phenolic hydroxyl group-containing resin has been proposed (see Patent Documents 4 and 5).

Japanese Examined Patent Publication No.59-52822 Japanese Patent Laid-Open No. 3-186847 Japanese Patent Laid-Open No. 11-237736 Japanese Patent No. 3960055 Japanese Patent No. 3812654

  By the way, in the resin containing a phenolic hydroxyl group, the phenolic hydroxyl group remains even after the curing treatment. Thereby, for example, since the amount of warpage of the silicon wafer with a cured film changes due to a large difference in the residual stress of the cured film between the normal time and the dry time, there may be an adverse effect on the process in that a conveyance error or the like occurs. However, from the viewpoint of pattern processability with an aqueous alkali solution, a phenolic hydroxyl group is required.

As described above, a photosensitive material that satisfies both pattern processability with an aqueous alkaline solution and suppressing a change in residual stress of the cured film has not been obtained.
Further, when a photosensitive material is used as a base rewiring layer insulating film at the time of bump formation, resistance to an alkaline chemical such as a resist stripping solution is also required.

  In view of the present situation, the problem to be solved by the present invention is to solve the above-mentioned problems caused by the phenolic hydroxyl group, to enable alkali development, and to change the residual stress due to the presence or absence of moisture in the environment (change in the amount of warping). ) Is small, and it is providing the photosensitive resin composition which can obtain the cured film which has high chemical resistance with respect to an alkaline chemical | drug | medicine.

  As a result of diligent research to solve the above problems, the present inventors have previously latented in the photosensitive resin composition a compound that can react with the phenolic hydroxyl group of the resin, and the alkali development with the phenolic hydroxyl group. In the curing process, the phenolic hydroxyl group of the resin is reacted with the above compound by heat to convert it into a structure that is stable against moisture in the environment, thereby reducing the change in residual stress, and this In addition to the above, by further combining a crosslinking agent, the film was finally hydrophobized and densified to find a photosensitive resin composition having excellent chemical resistance as a cured film. That is, the present invention has the following configuration.

｛式中、Ｒ₂は、ハロゲン原子；ニトロ基；シアノ基；不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；炭素数６〜２０の芳香族基；又は、下記一般式群（３）：

（式中、Ｒ_3、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子；不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；又は炭素数６〜２０の芳香族基；を表し、Ｒ₆は、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；又は炭素数６〜２０の芳香族基；を表す。）のいずれかで表される基；を表し、
Ｙは、不飽和結合を有していてもよい炭素数２〜１０の脂肪族基；炭素数３〜２０の脂環式基；繰り返し単位数が１〜２０の整数であるエチレンオキシド基；又は芳香族基；を有する有機基；を表し、
但し、Ｒ₂，Ｒ₃，Ｒ₄，Ｒ_5、Ｒ₆及びＹにおいて、水素原子がハロゲン原子、カルボキシル基、ニトロ基及びシアノ基からなる群から選ばれる少なくとも１つで置換されていてもよく、
ａは、１〜１０００の整数であり、
ｎは、１〜３の整数であり、そして
ｑは、０〜３の整数である。｝
で表される繰り返し構造を有するフェノール樹脂である、上記［１］〜［４］のいずれかに記載の感光性樹脂組成物。
［６］ 前記一般式（２）におけるＹが、下記一般式（４）：

｛式中、Ｒ₇〜Ｒ₁₀は、それぞれ独立に、水素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表す。｝
で表される基、又は下記一般式（５）：

｛式中、Ｒ₁₁〜Ｒ₁₄は、それぞれ独立に、水素原子；又はフッ素で置換されてもよい炭素数１〜１０の脂肪族基；を表し、Ｚは、単結合；フッ素で置換されてもよい炭素数１〜１０の脂肪族基；フッ素で置換されてもよい炭素数３〜２０の脂環式基；繰り返し単位数１〜２０のエチレンオキシド基；又は下記式群（６）：

のいずれかで表される基；を表す。｝
で表される基である、上記［５］に記載の感光性樹脂組成物。
［７］ 前記一般式（２）におけるＹが、下記一般式（７）：

｛式中、Ｗは、単結合；フッ素で置換されてもよい炭素数１〜１０の脂肪族基；フッ素で置換されてもよい炭素数３〜２０の脂環式基；繰り返し単位数１〜２０のエチレンオキシド基；又は下記式群（８）：

のいずれかで表される基；を表す。｝
で表される基である、上記［６］に記載の感光性樹脂組成物。
［８］ 前記（ｂ）化合物が、下記一般式（９）〜（１９）：

｛式中、Ｒ₁₅〜Ｒ₂₆及びＭ₁〜Ｍ₇は、それぞれ独立に１価の有機基を示し、そしてＸはハロゲン原子を示す。｝
からなる群から選ばれる１種以上の化合物である、上記［１］〜［７］のいずれかに記載の感光性樹脂組成物。
［９］ 前記（ｂ）化合物が、前記一般式（９）〜（１９）における、Ｒ₁₅〜Ｒ₂₆の炭素数が１〜２０である上記［８］に記載の感光性樹脂組成物。
［１０］ 前記（ｂ）化合物が、前記一般式（９）で表され、Ｒ₁₅が炭素数３〜１５であり、不飽和基を有する１価の脂肪族基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１１］ 前記（ｂ）化合物が、前記一般式（１０）で表され、Ｒ₁₆が水酸基を有する炭素数１〜１０の１価の脂肪族基、又は炭素数１〜１０の脂肪族基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１２］ 前記（ｂ）化合物が、前記一般式（１１）で表され、Ｒ₁₇が炭素数２〜１５の１価の有機基であり、Ｍ₁が炭素数が２〜１５の１価の有機基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１３］ 前記（ｂ）化合物が、前記一般式（１２）で表され、Ｒ₁₈及びＭ₂がそれぞれ独立に炭素数１〜１０の１価の有機基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１４］ 前記（ｂ）化合物が、前記一般式（１３）で表され、Ｒ₁₉が炭素数１〜１０の１価の有機基であり、Ｘが塩素、臭素又はヨウ素である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１５］ 前記（ｂ）化合物が、前記一般式（１４）で表され、Ｒ₂₀及びＭ₃がそれぞれ独立に炭素数１〜１０の１価の有機基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１６］ 前記（ｂ）化合物が、前記一般式（１５）で表され、Ｒ₂₁が炭素数１〜１０の１価の有機基であり、Ｒ₂₂が水素又は炭素数１〜１０の１価の有機基であり、Ｍ₄が水素又は炭素数が１〜５の１価の有機基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１７］ 前記（ｂ）化合物が、前記一般式（１６）で表され、Ｒ₂₃が炭素数６〜１５の１価の芳香族基であり、Ｍ₅が水素又は炭素数１〜１０の１価の有機基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１８］ 前記（ｂ）化合物が、前記一般式（１７）で表され、Ｒ₂₄が炭素数１〜１２の１価の有機基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［１９］ 前記（ｂ）化合物が、前記一般式（１８）で表され、Ｒ₂₅及びＭ₆がそれぞれ独立に炭素数１〜１０の１価の有機基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［２０］ 前記（ｂ）化合物が、前記一般式（１９）で表され、Ｒ₂₆及びＭ₇がそれぞれ独立に炭素数１〜１０の１価の有機基である化合物を含む、上記［８］に記載の感光性樹脂組成物。
［２１］ 上記［１］〜［２０］のいずれかに記載の感光性樹脂組成物を基板に塗布する工程、
該感光性樹脂組成物を露光する工程、
該露光の後の感光性樹脂組成物を現像してレリーフパターンを形成する工程、及び
該レリーフパターンを加熱して硬化レリーフパターンを形成する工程
を含む、硬化レリーフパターンの製造方法。
［２２］ 上記［２１］に記載の硬化レリーフパターンの製造方法により得られる硬化レリーフパターンを有して成る、半導体装置。 [1] (a) a resin having a phenolic hydroxyl group,
(B) a compound having only one group that reacts with the phenolic hydroxyl group of the resin (a) and satisfying the following formula (1):
(C) a photosensitive compound, and (d) a crosslinking agent,
A photosensitive resin composition comprising:
0.2 ≦ (C−D) / C− (A−B) / A ≦ 1 (1)
(In the formula, A, B, C, and D are normalized peak intensities corresponding to OH stretching vibrations at 3,000 to 4,000 cm ⁻¹ of the infrared absorption spectrum, respectively, and A is (a) The peak intensity measured only with B, B is the peak intensity measured only after heating in an inert gas atmosphere at 250 ° C. for 1 hour, and C is the peak measured with the mixture of (a) and (b). Intensity, D indicates the peak intensity measured after heating at 250 ° C. for 1 hour in an inert gas atmosphere for the mixture of (a) and (b), respectively.
[2] The photosensitive resin composition according to the above [1], wherein the resin (a) having a phenolic hydroxyl group is a phenol resin.
[3] The (d) cross-linking agent includes two or more —N— (CH ₂ —OR) groups (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). }, Two or more —C— (CH ₂ —OR) groups {wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. }, A compound having two or more epoxy groups, a compound having two or more isocyanate groups, a compound obtained by reacting two or more isocyanate groups with an alcohol, oxime or pyrazole, two or more oxazolyls The photosensitive resin composition according to the above [1] or [2], which is one or more compounds selected from the group consisting of a compound having a group and a compound having two or more unsaturated bonds.
[4] The photosensitive resin composition according to any one of [1] to [3], which is used for forming a semiconductor protective film or for forming an interlayer insulating film.
[5] The resin (a) having a phenolic hydroxyl group is represented by the following general formula (2):

{In the formula, R ₂ represents a halogen atom; a nitro group; a cyano group; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; 6-20 aromatic groups; or the following general formula group (3):

(In the formula, R _3, R ₄ and R ₅ are each independently a hydrogen atom; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms, and R ₆ is an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms; a group represented by any one of
Y represents an aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; an ethylene oxide group having an integer of 1 to 20 repeating units; or aromatic An organic group having a group;
However, in R ₂ , R ₃ , R ₄ , R _5, R ₆ and Y, the hydrogen atom may be substituted with at least one selected from the group consisting of a halogen atom, a carboxyl group, a nitro group and a cyano group. ,
a is an integer of 1-1000,
n is an integer of 1 to 3, and q is an integer of 0 to 3. }
The photosensitive resin composition in any one of said [1]-[4] which is a phenol resin which has a repeating structure represented by these.
[6] Y in the general formula (2) is the following general formula (4):

{Wherein, R _{7 to} R ₁₀ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine. }
Or a group represented by the following general formula (5):

{Wherein, R _{11 to} R ₁₄ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; Z represents a single bond; substituted with fluorine; An aliphatic group having 1 to 10 carbon atoms; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; an ethylene oxide group having 1 to 20 repeating units; or the following formula group (6):

A group represented by any one of the following: }
The photosensitive resin composition as described in said [5] which is group represented by these.
[7] Y in the general formula (2) is the following general formula (7):

{Wherein W is a single bond; an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; 20 ethylene oxide groups; or the following formula group (8):

A group represented by any one of the following: }
The photosensitive resin composition as described in said [6] which is group represented by these.
[8] The compound (b) is represented by the following general formulas (9) to (19):

{In the formula, R _{15 to} R ₂₆ and M _{1 to} M ₇ each independently represent a monovalent organic group, and X represents a halogen atom. }
The photosensitive resin composition in any one of said [1]-[7] which is 1 or more types of compounds chosen from the group which consists of.
[9] The photosensitive resin composition according to [8], wherein the compound (b) has 1 to 20 carbon atoms of R _{15 to} R ₂₆ in the general formulas (9) to (19).
[10] The above-mentioned compound (b) includes the compound represented by the general formula (9), wherein R ₁₅ is a monovalent aliphatic group having 3 to ₁₅ carbon atoms and having an unsaturated group. 8]. The photosensitive resin composition as described in 8].
[11] The compound (b) is represented by the general formula (10), and R ₁₆ is a monovalent aliphatic group having 1 to 10 carbon atoms having a hydroxyl group, or an aliphatic group having 1 to 10 carbon atoms. The photosensitive resin composition according to the above [8], comprising a compound.
[12] The compound (b) is represented by the general formula (11), R ₁₇ is a monovalent organic group having 2 to 15 carbon atoms, and M ₁ is a monovalent organic group having 2 to 15 carbon atoms. The photosensitive resin composition according to the above [8], comprising a compound that is an organic group.
[13] The above [8], wherein the compound (b) includes a compound represented by the general formula (12), wherein R ₁₈ and M ₂ are each independently a monovalent organic group having 1 to 10 carbon atoms. The photosensitive resin composition as described in 2.
[14] The compound (b) includes the compound represented by the general formula (13), R ₁₉ is a monovalent organic group having 1 to 10 carbon atoms, and X is chlorine, bromine, or iodine. The photosensitive resin composition as described in [8] above.
[15] The above [8], wherein the compound (b) includes a compound represented by the general formula (14), wherein R ₂₀ and M ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. The photosensitive resin composition as described in 2.
[16] The compound (b) is represented by the general formula (15), R ₂₁ is a monovalent organic group having 1 to 10 carbon atoms, and R ₂₂ is hydrogen or monovalent having 1 to 10 carbon atoms. The photosensitive resin composition as described in [8] above, which comprises a compound wherein M ₄ is hydrogen or a monovalent organic group having 1 to 5 carbon atoms.
[17] The compound (b) is represented by the general formula (16), R ₂₃ is a monovalent aromatic group having 6 to 15 carbon atoms, and M ₅ is hydrogen or 1 having 1 to 10 carbon atoms. The photosensitive resin composition as described in said [8] containing the compound which is a valent organic group.
[18] The photosensitive resin according to [8], wherein the compound (b) includes a compound represented by the general formula (17), and R ₂₄ is a monovalent organic group having 1 to 12 carbon atoms. Composition.
[19] The above [8], wherein the compound (b) includes a compound represented by the general formula (18), wherein R ₂₅ and M ₆ are each independently a monovalent organic group having 1 to 10 carbon atoms. The photosensitive resin composition as described in 2.
[20] The above [8], wherein the compound (b) includes a compound represented by the general formula (19), wherein R ₂₆ and M ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms. The photosensitive resin composition as described in 2.
[21] A step of applying the photosensitive resin composition according to any one of [1] to [20] to a substrate,
Exposing the photosensitive resin composition;
A method for producing a cured relief pattern, comprising: developing a photosensitive resin composition after the exposure to form a relief pattern; and heating the relief pattern to form a cured relief pattern.
[22] A semiconductor device comprising a cured relief pattern obtained by the method for producing a cured relief pattern according to [21].

  According to the photosensitive resin composition of the present invention, alkali development is possible, the change in residual stress (change in the amount of warpage) due to the presence or absence of moisture in the environment is small, and it has high chemical resistance against alkaline chemicals. A cured film can be obtained. For example, a semiconductor protective film or an interlayer insulating film can be suitably formed on the obtained cured film.

  Hereinafter, typical embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments.

<Photosensitive resin composition>
One embodiment of the present invention provides:
(A) a resin having a phenolic hydroxyl group,
(B) a compound having only one group that reacts with the phenolic hydroxyl group of the resin (a) and satisfying the following formula (1) (hereinafter referred to as “(b) compound”)
(C) a photosensitive compound, and (d) a crosslinking agent,
A photosensitive resin composition comprising:
0.2 ≦ (C−D) / C− (A−B) / A ≦ 1 (1)
(In the formula, A, B, C, and D are normalized peak intensities corresponding to OH stretching vibrations at 3,000 to 4,000 cm ⁻¹ of the infrared absorption spectrum, respectively, and A is (a) The peak intensity measured only with B, B is the peak intensity measured only after heating in an inert gas atmosphere at 250 ° C. for 1 hour, and C is the peak measured with the mixture of (a) and (b). Intensity, D indicates the peak intensity measured after heating at 250 ° C. for 1 hour in an inert gas atmosphere for the mixture of (a) and (b), respectively.
The above (C−D) / C− (A−B) / A is also referred to as “hydroxyl group modification rate E” below.

[Hydroxyl modification rate E]
In the photosensitive resin composition according to one embodiment of the present invention, the resin (a) having a phenolic hydroxyl group and the compound (b) are latent in advance in the photosensitive resin composition. Thereby, in the curing step, the phenolic hydroxyl group of the resin can be converted to a structure stable against moisture in the environment by reacting with the above compound by heat. The compound (b) in the photosensitive resin composition has the ability to react so as to give a predetermined range of hydroxyl group modification rate. That the hydroxyl group modification rate can be controlled within a predetermined range means that the amount of decrease in phenolic hydroxyl groups when the photosensitive resin composition is cured can be controlled. Thereby, the residual amount of phenolic hydroxyl group can be kept low after curing while maintaining the amount of phenolic hydroxyl group in the photosensitive resin composition and maintaining good aqueous alkali solubility. In one embodiment of the present invention, the hydroxyl group modification rate is evaluated as a hydroxyl group modification rate E measured under predetermined conditions.

  In order to show the modification rate of the OH group, an infrared absorption (IR) spectrum can be used. In the infrared region, OH groups absorb a wide range of stretching vibrations. By determining the rate at which this peak intensity changes before and after the reaction, the modification rate of OH groups can be evaluated. Here, the peak intensity refers to a numerical value represented by absorbance based on the baseline of the IR spectrum.

  A transmission method is preferred as a method for measuring the peak intensity of the IR spectrum. The measurement is always performed in a chamber in which dry air is flowing. This is because the peak intensity of the OH group is affected by the humidity in the air. Crystals for sample application used in the transmission method include substances that do not absorb in the infrared absorption band and are less affected by humidity, such as silicon or germanium substrates, and barium fluoride, calcium fluoride, sodium fluoride, etc. Alkali salt crystals are preferably used. Among these, barium fluoride is particularly preferable because of the stability of the baseline.

  Hydroxyl modification rate E is determined by: (a) a solution of a resin having a phenolic hydroxyl group (hereinafter also referred to as a resin alone), a mixture of (a) a resin having a phenolic hydroxyl group, and (b) a compound (hereinafter referred to as a mixture). The solution is used for evaluation. First, these are each coated on a crystal for coating a sample, and then heated and dried at around 90 to 120 ° C. to prepare a coating film. First, the IR of each coating film is measured. Next, each coating film is heated in an inert gas atmosphere at 250 ° C. for 1 hour, and IR measurement is performed under the same conditions as before heating. In view of the actual use conditions, the coating film after preparation is made as it is for the resin alone, the mixture is allowed to proceed with a substitution reaction by light and / or heat, and both are assumed to be cured conditions (for example, IR measurement is performed on the coating film cured by heating in an inert gas atmosphere (typically under an inert gas stream) at a temperature of 180 to 350 ° C., and the measured value obtained and the cure Ideally, the hydroxyl group modification rate is calculated from the measured values before (for the resin alone) and before the substitution reaction (for the mixture). However, in the present invention, for convenience, the hydroxyl group modification rate E is evaluated by adopting 250 ° C. and 1 hour heating conditions as model conditions. The inert gas atmosphere can be, for example, a nitrogen atmosphere.

Next, it is confirmed that the whole baseline is horizontal in the spectrum with the absorbance on the vertical axis. The distance from the baseline to the peak top is the absorbance. About the OH group (3,000 to 4,000 cm ^-1 OH stretching vibration), the absorbance before and after heating the resin alone (this is assumed to be before and after curing), and before and after heating the mixture (this is before and after the substitution reaction and curing) The value normalized by dividing by the absorbance of the phenyl group in the same spectrum (usually a peak near 1,600 cm ⁻¹ ) is obtained as the normalized peak intensity. The values of the single resin are A (before heating) and B (after heating at 250 ° C. and 1 hour), and the values of the mixture are C (before heating) and D (after heating at 250 ° C. and 1 hour). Following formula:
Hydroxyl modification rate E = (C−D) / C− (A−B) / A
Thus, the hydroxyl group modification rate E is obtained.

  In the photosensitive resin composition which concerns on 1 aspect of this invention, the value of the hydroxyl group modification rate E calculated | required as mentioned above is the range of 0.2-1. If the hydroxyl group modification rate E is 0.2 or more, the effect of reducing the difference in residual stress and improving chemical resistance is sufficient, and 1.0 is the maximum value by definition. The hydroxyl group modification rate E is preferably in the range of 0.3 to 1.0, more preferably in the range of 0.4 to 1.0.

  The inventors speculate that the effect of the present application is achieved when the value of the hydroxyl group modification rate E is in the range of 0.2 to 1 as follows.

  Since the photosensitive resin composition of the present invention has a phenolic hydroxyl group contained in the component (a), a relief pattern can be formed using an alkali developer. On the other hand, in the curing step, the phenolic hydroxyl group contained in the component (a) is modified by a thermal reaction, and the cured film obtained from the photosensitive resin composition has a reduced number of phenolic hydroxyl groups than that during development. A thing with high property can be obtained. Therefore, the semiconductor device to which the cured film obtained from the photosensitive resin composition is applied has a condition in which moisture exists under normal temperature and normal pressure, and a condition in which moisture hardly exists under high vacuum such as during sputtering. The difference in residual stress between the two is small, that is, the change in the amount of warpage is small. If the change in the amount of warpage is small, the manufacturing yield of the semiconductor device is improved. Moreover, the cured film obtained has chemical resistance against alkaline chemicals frequently used in the semiconductor device manufacturing process due to a synergistic effect of the phenolic hydroxyl group modification reaction and the crosslinking agent crosslinking reaction.

[(A) Resin having phenolic hydroxyl group]
(A) As a resin having a phenolic hydroxyl group, a phenol resin, a phenol novolak resin, a cresol novolak resin, a polyhydroxy aromatic vinyl, a polyhydroxyamide, a polyhydroxyimide, a polyamic acid ester, and phenols are subjected to addition condensation. Polymerize directly by reactions such as polycondensation, polyaddition, oxidative coupling polymerization, addition polymerization (radical, anion, cation, or coordination), or modify the polymer with phenols to introduce phenolic hydroxyl groups. However, it is not limited. These may be used alone, or may be blended or copolymerized.

｛式中、Ｒ₂は、ハロゲン原子；ニトロ基；シアノ基；不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；炭素数６〜２０の芳香族基；又は、下記一般式群（３）：

（式中、Ｒ_3、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子；不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；又は炭素数６〜２０の芳香族基；を表し、Ｒ₆は、不飽和結合を有していてもよい炭素数１〜１０の脂肪族基；炭素数３〜２０の脂環式基；又は炭素数６〜２０の芳香族基；を表す。）のいずれかで表される基；を表し、
Ｙは、不飽和結合を有していてもよい炭素数２〜１０の脂肪族基；炭素数３〜２０の脂環式基；繰り返し単位数が１〜２０の整数であるエチレンオキシド基；又は芳香族基を有する有機基；を表し、
但し、Ｒ₂，Ｒ₃，Ｒ₄，Ｒ_5、Ｒ₆及びＹにおいて、水素原子がハロゲン原子、カルボキシル基、ニトロ基及びシアノ基からなる群から選ばれる少なくとも１つで置換されていてもよく、
ａは、１〜１０００の整数であり、
ｎは、１〜３の整数であり、そして
ｑは、０〜３の整数である。｝
で表される繰り返し構造を有する。 (A) The resin having a phenolic hydroxyl group preferably has the following general formula (2) from the viewpoint of low dielectric constant and excellent elongation during low-temperature curing.

{In the formula, R ₂ represents a halogen atom; a nitro group; a cyano group; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; 6-20 aromatic groups; or the following general formula group (3):

(In the formula, R _3, R ₄ and R ₅ are each independently a hydrogen atom; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms, and R ₆ is an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms; a group represented by any one of
Y represents an aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; an ethylene oxide group having an integer of 1 to 20 repeating units; or aromatic An organic group having a group;
However, in R ₂ , R ₃ , R ₄ , R _5, R ₆ and Y, the hydrogen atom may be substituted with at least one selected from the group consisting of a halogen atom, a carboxyl group, a nitro group and a cyano group. ,
a is an integer of 1-1000,
n is an integer of 1 to 3, and q is an integer of 0 to 3. }
It has the repeating structure represented by these.

In the above general formula (2), preferred examples of R ₂ include methyl group, halogen atom, trifluoromethyl group, nitro group, cyano group, acetyl group, phenylcarbonyl group, carboxyl group, ester from the viewpoint of alkali solubility. Groups, amide groups, and imide groups. Particularly preferred examples are fluorine atom, trifluoromethyl group, carboxyl group, ester group, and imide group.

  Q in the general formula (2) is an integer of 0 to 3, and is preferably 0 or 1 from the viewpoint of reactivity at the time of polymer synthesis.

｛式中、Ｒ₇、Ｒ₈、Ｒ₉及びＲ₁₀は、それぞれ独立に、水素原子；又はフッ素で置換されていてもよい炭素数１〜１０の脂肪族基；を表す。｝

｛式中、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃及びＲ₁₄は、それぞれ独立に、水素原子；又はフッ素で置換されていてもよい炭素数１〜１０の脂肪族基；を表し、
Ｚは、単結合；フッ素で置換されていてもよい炭素数１〜１０の脂肪族基；フッ素で置換されていてもよい炭素数３〜２０の脂環式基；繰り返し単位数１〜２０のエチレンオキシド基；又は、下記式群（６）：

のいずれかで表される２価の基；を表す。｝
で表される基が挙げられる。 As a preferable example of Y, from the viewpoint of toughness of the film after curing, the following general formula (4) or (5):

{Wherein R ₇ , R ₈ , R ₉ and R ₁₀ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine. }

{Wherein R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine;
Z is a single bond; an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; Ethylene oxide group; or the following formula group (6):

A divalent group represented by any of the following: }
The group represented by these is mentioned.

｛式中、Ｗは、上記Ｚと同義である。｝
で表される構造が好ましい。 Examples of the structure represented by the general formula (5) include the following general formula (7):

{Wherein W has the same meaning as Z above. }
The structure represented by these is preferable.

  More preferred examples of Y are p-xylylene group, 4,4'-dimethylenebiphenyl group, and bis (4-methylenephenyl) ether group.

a is 1 or more from the viewpoint of toughness of the film after curing, and 1000 or less from the viewpoint of alkali solubility, and is preferably an integer of 1 to 30.
n is preferably 2 or 3 from the viewpoint of alkali solubility.

  (A) The weight average molecular weight of the resin having a phenolic hydroxyl group is preferably 700 to 100,000, more preferably 1,500 to 80,000, and still more preferably 2,000 to 50,000. . The weight average molecular weight is preferably 700 or more from the viewpoint of elongation, and preferably 100,000 or less from the viewpoint of alkali solubility of the composition.

  The weight average molecular weight can be measured by gel permeation chromatography (GPC) and can be calculated from a calibration curve prepared using standard polystyrene.

  (A) A resin having a phenolic hydroxyl group has a condensation component (for example, an aldehyde compound, a ketone compound, a methylol compound, an alkoxymethyl compound, a diene compound, or a haloalkyl compound) with respect to phenol and / or a phenol derivative as shown below. It can be obtained by polymerization. From the viewpoint of reaction control and the stability of the obtained (a) resin having a phenolic hydroxyl group and the stability of the photosensitive resin composition, the charged molar ratio of the phenol compound to the condensation component is 5: 1 to 1.01: 1 is preferable, and more preferably 2.5: 1 to 1.1: 1.

  The above (a) phenol and phenol derivatives that can be used to obtain a resin having a phenolic hydroxyl group include cresol, ethylphenol, propylphenol, butylphenol, amylphenol, cyclohexylphenol, hydroxybiphenyl, benzylphenol, and nitrobenzyl. Phenol, cyanobenzylphenol, adamantanephenol, xylenol, nitrophenol, fluorophenol, chlorophenol, bromophenol, trifluoromethylphenol, N- (hydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- ( Hydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboximide, trifluoromethylphenol, hydroxybenzoic acid, Methyl droxybenzoate, ethyl hydroxybenzoate, benzyl hydroxybenzoate, hydroxybenzamide, hydroxybenzaldehyde, hydroxyacetophenone, hydroxybenzophenone, hydroxybenzonitrile, catechol, methylcatechol, ethylcatechol, hexylcatechol, benzylcatechol, nitrobenzylcatechol, resorcinol , Methyl resorcinol, ethyl resorcinol, hexyl resorcinol, benzyl resorcinol, nitrobenzyl resorcinol, hydroquinone, caffeic acid, dihydroxybenzoic acid, methyl dihydroxybenzoate, ethyl dihydroxybenzoate, benzyl dihydroxybenzoate, dihydroxybenzamide, dihydroxybenzaldehyde, dihydroxy Acetophenone, dihydroxybenzophenone, dihydroxybenzonitrile, N- (dihydroxyphenyl) -5-norbornene-2,3-dicarboximide, N- (dihydroxyphenyl) -5-methyl-5-norbornene-2,3-dicarboximide , Nitrocatechol, fluorocatechol, chlorocatechol, bromocatechol, trifluoromethylcatechol, nitroresorcinol, fluororesorcinol, chlororesorcinol, bromoresorcinol, trifluoromethylresorcinol, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene , Trihydroxybenzoic acid, methyl trihydroxybenzoate, ethyl trihydroxybenzoate, benzyl trihydroxybenzoate, trihydroxybenzoate Examples thereof include benzamide, trihydroxybenzaldehyde, trihydroxyacetophenone, trihydroxybenzophenone, and trihydroxybenzonitrile.

  Examples of the aldehyde compound include acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethyl butyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2-carboxaldehyde, Examples include malondialdehyde, succinaldehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, and terephthalaldehyde.

  Examples of the ketone compound include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, dicyclohexyl ketone, dibenzyl ketone, cyclopentanone, cyclohexanone, bicyclohexanone, cyclohexanedione, 3-butyn-2-one, 2-norbornanone, and adamantanone. 2,2-bis (4-oxocyclohexyl) propane and the like.

  Examples of the methylol compound include 1,3-bis (hydroxymethyl) urea, ribitol, arabitol, allitol, 2,2-bis (hydroxymethyl) butyric acid, 2-benzyloxy-1,3-propanediol, 2,2- Dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, monoacetin, 2-methyl-2-nitro-1,3-propanediol, 5-norbornene-2,2-dimethanol, 5-norbornene-2,3-dimethanol, pentaerythritol, 2-phenyl-1,3-propanediol, trimethylolethane, trimethylolpropane, 3,6-bis (hydroxymethyl) durene, 2-nitro-p- Xylylene glycol, 1,10-dihydroxydecane, 1,12-dihydroxydode 1,4-bis (hydroxymethyl) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexene, 1,6-bis (hydroxymethyl) adamantane, 1,4-benzenedimethanol, 1,3-benzenedimethanol 2,6-bis (hydroxymethyl) -p-cresol, 2,6-bis (hydroxymethyl) -1,4-dimethoxybenzene, 2,3-bis (hydroxymethyl) naphthalene, 2,6-bis (hydroxy Methyl) naphthalene, 1,8-bis (hydroxymethyl) anthracene, 2,2′-bis (hydroxymethyl) diphenyl ether, 4,4′-bis (hydroxymethyl) diphenyl ether, 4,4′-bis (hydroxymethyl) diphenyl Thioether, 4,4'-bis (hydroxymethyl) benzopheno 4-hydroxymethylbenzoic acid-4′-hydroxymethylphenyl, 4-hydroxymethylbenzoic acid-4′-hydroxymethylanilide, 4,4′-bis (hydroxymethyl) phenylurea, 4,4′-bis (hydroxy Methyl) phenylurethane, 1,8-bis (hydroxymethyl) anthracene, 4,4′-bis (hydroxymethyl) biphenyl, 2,2′-dimethyl-4,4′-bis (hydroxymethyl) biphenyl, 2,2 -Bis (4-hydroxymethylphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and the like.

  Examples of the alkoxymethyl compound include 1,3-bis (methoxymethyl) urea, 2,2-bis (methoxymethyl) butyric acid, 2,2-bis (methoxymethyl) -5-norbornene, and 2,3-bis (methoxy). Methyl) -5-norbornene, 1,4-bis (methoxymethyl) cyclohexane, 1,4-bis (methoxymethyl) cyclohexene, 1,6-bis (methoxymethyl) adamantane, 1,4-bis (methoxymethyl) benzene 1,3-bis (methoxymethyl) benzene, 2,6-bis (methoxymethyl) -p-cresol, 2,6-bis (methoxymethyl) -1,4-dimethoxybenzene, 2,3-bis (methoxy) Methyl) naphthalene, 2,6-bis (methoxymethyl) naphthalene, 1,8-bis (methoxymethyl) anthracene, 2,2 -Bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl ether, 4,4'-bis (methoxymethyl) diphenyl thioether, 4,4'-bis (methoxymethyl) benzophenone, 4-methoxymethyl benzoate Acid-4′-methoxymethylphenyl, 4-methoxymethylbenzoic acid-4′-methoxymethylanilide, 4,4′-bis (methoxymethyl) phenylurea, 4,4′-bis (methoxymethyl) phenylurethane, 1 , 8-bis (methoxymethyl) anthracene, 4,4′-bis (methoxymethyl) biphenyl, 2,2′-dimethyl-4,4′-bis (methoxymethyl) biphenyl, 2,2-bis (4-methoxy) Methylphenyl) propane, ethylene glycol dimethyl ether, diethylene Recall dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol dimethyl ether, tetrapropylene glycol dimethyl ether.

  Examples of the diene compound include butadiene, pentadiene, hexadiene, heptadiene, octadiene, 3-methyl-1,3-butadiene, 1,3-butanediol-dimethacrylate, 2,4-hexadien-1-ol, and methylcyclohexadiene. , Cyclopentadiene, cyclohexadiene, cyclohexadiene, cyclooctadiene, dicyclopentadiene, 1-hydroxydicyclopentadiene, 1-methylcyclopentadiene, methyldicyclopentadiene, diallyl ether, diallyl sulfide, diallyl adipate, 2,5- Norbornadiene, tetrahydroindene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, triallyl cyanurate, diallyl isocyanurate, triallyl isocyanurate, Soshianuru acid diallyl propyl and the like.

  Examples of the haloalkyl compound include xylene dichloride, bischloromethyldimethoxybenzene, bischloromethyldurene, bischloromethylbiphenyl, bischloromethyl-biphenylcarboxylic acid, bischloromethyl-biphenyldicarboxylic acid, bischloromethyl-methylbiphenyl, Examples include bischloromethyl-dimethylbiphenyl, bischloromethylanthracene, ethylene glycol bis (chloroethyl) ether, diethylene glycol bis (chloroethyl) ether, triethylene glycol bis (chloroethyl) ether, tetraethylene glycol bis (chloroethyl) ether, and the like.

  Although the above-mentioned phenol or phenol derivative can be polymerized while dehydrating or dealcoholating or cleaving the unsaturated bond, a resin can be used. Acidic catalysts include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, methanesulfonic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, acetic acid, oxalic acid, 1-hydroxyethylidene-1,1′-diphosphone Examples thereof include acid, zinc acetate, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, and the like. On the other hand, alkaline catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, sodium carbonate, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, piperidine, piperazine, 1 , 4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, ammonia, hexa And methylenetetramine.

  (A) When performing the synthetic reaction of resin which has a phenolic hydroxyl group, an organic solvent can be used as needed. Specific examples of organic solvents that can be used include bis (2-methoxyethyl) ether, methyl cellosolve, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone, Examples include toluene, xylene, γ-butyrolactone, N-methyl-2-pyrrolidone, but are not limited thereto. The amount of the organic solvent used is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass with respect to 100 parts by mass of the total mass of the raw materials charged. Moreover, reaction temperature is 40-250 degreeC normally, and the range of 100-200 degreeC is more preferable. The reaction time is usually 1 to 10 hours.

  (A) The resin having a phenolic hydroxyl group may be a copolymer of a plurality of components. In this case, as the copolymer component, a compound having no phenolic hydroxyl group may be used in addition to phenol and / or a phenol derivative.

[(B) Compound capable of reacting with phenolic hydroxyl group contained in (a) resin ((b) compound)]
(B) A compound is a compound in which at least any of an etherification reaction, esterification reaction, and a urethanation reaction with a phenolic hydroxyl group is possible, for example. These reactions may be single reactions or a plurality of reactions may be combined.

｛式中、Ｒ₁₅〜Ｒ₂₆、Ｍ₁〜Ｍ₇は、それぞれ独立に１価の有機基を示し、そしてＸはハロゲン原子を示す。｝
からなる群から選ばれる１種以上の化合物が挙げられる。これらの化合物によれば、（ａ）フェノール性水酸基を有する樹脂と（ｂ）化合物との間で、エーテル化反応、エステル化反応、及びウレタン化反応の少なくともいずれかを進行させることができる。 Specific examples of the compound (b) include alcohol, carboxylic acid, carboxylic acid ester, carboxylic acid anhydride, acid halide, carbonate ester, amino compound, methylol compound, isocyanate, block isocyanate, sulfate ester and the like. Among these, as preferred examples, the following general formulas (9) to (19):

{Wherein, R _{15 to} R ₂₆ and M _{1 to} M ₇ each independently represent a monovalent organic group, and X represents a halogen atom. }
One or more compounds selected from the group consisting of: According to these compounds, at least one of an etherification reaction, an esterification reaction, and a urethanization reaction can proceed between (a) a resin having a phenolic hydroxyl group and (b) the compound.

  These reactants can be used in combination with at least one of a catalyst such as an acid, a base and metals, and a condensing agent and a dehydrating agent. For example, when alcohol is reacted with diethyl azodicarboxylate and triphenylphosphine, etherification can proceed efficiently (that is, Mitsunobu reaction).

R _{15 to} R ₂₆ are preferably an aliphatic group, an alicyclic group or an aromatic group having 1 to 20 carbon atoms. R _{15 to} R ₂₆ may contain, for example, a carbonyl group, an ether group, a sulfide group, or a sulfone group.

In a preferred example of the alcohol, the compound (b) includes a compound represented by the general formula (9), wherein R ₁₅ is a monovalent aliphatic group having an unsaturated group. Such a compound is advantageous in that the mechanical properties can be further enhanced by inducing a cross-linking reaction between molecules and a cyclization reaction in the molecule after the substitution reaction.

As the reaction between the phenolic hydroxyl group and the alcohol, a reaction in which the hydroxyl group is substituted and etherified can be considered. Examples of the alcohol include propanol, butanol, pentanol, hexanol, heptanol, octanol, allyl alcohol, benzyl alcohol, cyclohexanol, cyclohexenol, decenol, linalool and the like.
The reaction of the phenolic hydroxyl group in the resin with the alcohol is shown in the following formula.

In a preferred example of the carboxylic acid, the compound (b) includes a compound represented by the general formula (10), wherein R ₁₆ is a monovalent aliphatic group having a hydroxyl group, or an aliphatic group. Such a compound is advantageous in that it can induce a cross-linking reaction between molecules and a cyclization reaction in the molecule after the substitution reaction, and can further increase mechanical properties.

As the reaction between the phenolic hydroxyl group and the carboxylic acid, a reaction in which the hydroxyl group is substituted and esterified can be considered. Examples of the carboxylic acid include acetic acid, propionic acid, methacrylic acid, valeric acid, cyclohexanecarboxylic acid, benzoic acid, toluic acid and the like.
The reaction of the phenolic hydroxyl group in the resin with the carboxylic acid is shown in the following formula.

In a preferred example of the carboxylic acid ester, the compound (b) includes a compound represented by the general formula (11), wherein R ₁₇ and M ₁ are monovalent organic groups having 2 to 15 carbon atoms. Such a compound is advantageous in that a substitution reaction can be efficiently performed.

（Ｒ₂₇は、炭素数１〜１０の１価の有機基を示し、そしてＭ₈は炭素数１〜１０の１価の有機基を示す。）
の構造のβ−ケトエステルの場合、エステル化反応の後、カルボニル部分がさらにフェノールの芳香族と反応し、環化反応が起こりうるので、効率的に反応が起こると考えられ好ましい。カルボン酸エステルの例としては、酢酸エチル、安息香酸メチル、安息香酸エチル、サリチル酸メチル、アセト酢酸エチル、アセト酢酸プロピル等が挙げられるが、特にβ−ケトエステルであるアセト酢酸エチル、アセト酢酸プロピルなどが好ましい。
樹脂中のフェノール性水酸基とカルボン酸エステルとの反応を次式に示す。

As a reaction between the phenolic hydroxyl group and the carboxylic acid ester, a reaction in which an alkoxy group is substituted and esterified can be considered. In particular, the following general formula (20):

(R ₂₇ represents a monovalent organic group having 1 to 10 carbon atoms, and M ₈ represents a monovalent organic group having 1 to 10 carbon atoms.)
In the case of the β-ketoester having the structure, it is preferable that the carbonyl moiety further reacts with the aromatic of the phenol after the esterification reaction to cause a cyclization reaction. Examples of carboxylic acid esters include ethyl acetate, methyl benzoate, ethyl benzoate, methyl salicylate, ethyl acetoacetate, propyl acetoacetate, etc., and in particular, β-ketoesters such as ethyl acetoacetate and propyl acetoacetate. preferable.
The reaction between the phenolic hydroxyl group in the resin and the carboxylic acid ester is shown in the following formula.

In a preferred example of the carboxylic anhydride, the compound (b) includes a compound represented by the general formula (12), wherein R ₁₈ and M ₂ are each independently a monovalent organic group having 1 to 10 carbon atoms. . Such a compound is advantageous in that a substitution reaction can be efficiently performed.

As a reaction between a phenolic hydroxyl group and a carboxylic acid anhydride, a reaction of substitution and esterification can be considered. Examples of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, benzoic anhydride, phthalic anhydride, succinic anhydride, itaconic anhydride, maleic anhydride and the like.
The reaction between the phenolic hydroxyl group in the resin and the carboxylic anhydride is shown in the following formula.

In a preferred example of the acid halide, the compound (b) is a compound represented by the general formula (13), wherein R ₁₉ is a monovalent organic group having 1 to 20 carbon atoms, and X is chlorine, bromine or iodine. including. Such a compound is advantageous in that a substitution reaction can be efficiently performed.

As a reaction between a phenolic hydroxyl group and an acid halide, a reaction in which a halogen atom is substituted and esterified can be considered. Examples of acid halides include acetyl chloride, acetyl bromide, propionyl chloride, methacryloyl chloride, benzoyl chloride, benzoic acid chloride and the like.
The reaction between the phenolic hydroxyl group in the resin and the acid halide is shown in the following formula.

In a preferred example of the carbonate ester, the compound (b) includes a compound represented by the above general formula (14), wherein R ₂₀ is a methyl group and M ₃ is a monovalent organic group having 1 to 10 carbon atoms. Such a compound is advantageous in that a substitution reaction can be efficiently performed.

As a reaction between a phenolic hydroxyl group and a carbonate ester, a reaction in which an alkoxy group is substituted and carbonated can be considered, and when the reaction is further advanced, decarboxylation and etherification may be considered. Examples of the carbonate ester include dimethyl carbonate, diphenyl carbonate, dibenzyl carbonate, propylene carbonate, ethylene carbonate, allyl phenyl carbonate, t-butyl phenyl carbonate and the like.
The reaction between the phenolic hydroxyl group in the resin and the carbonate is shown in the following formula.

In a preferred example of the amino compound, the compound (b) is represented by the general formula (15), R ₂₁ is a monovalent organic group having 1 to 10 carbon atoms, R ₂₂ is hydrogen or monovalent having 1 to 15 carbon atoms. And a compound in which M ₄ is hydrogen or a monovalent organic group having 1 to 5 carbon atoms. Such a compound is advantageous in that a substitution reaction can be efficiently performed.

メチロール化合物の好ましい例において、（ｂ）化合物は、上記一般式（１６）で表され、Ｒ₂₃が炭素数６〜１５、Ｍ₅が水素又は炭素数１〜１０の１価の有機基である化合物を含む。このような化合物は効率的に置換反応を行うことが出来る点で有利である。 As a reaction between a phenolic hydroxyl group and an amino compound, a reaction in which an alkoxy group or a hydroxyl group is substituted and etherified is considered. Examples of such amino compounds include acetamide methanol, N- (hydroxymethyl) acrylamide, N, N′-dimethylaminomethyl ethyl ether, N-methylaminomethyl propyl ether, and the like.
The reaction between the phenolic hydroxyl group in the resin and the amino compound is shown in the following formula.

In a preferred example of the methylol compound, the compound (b) is represented by the general formula (16), R ₂₃ is a carbon number of 6 to 15, M ₅ is hydrogen or a monovalent organic group of 1 to 10 carbon atoms. Contains compounds. Such a compound is advantageous in that a substitution reaction can be efficiently performed.

As the reaction between the phenolic hydroxyl group and the methylol compound, a reaction in which an alkoxy group is substituted and etherified can be considered. Examples of methylol compounds include benzyl methyl ether, benzyl allyl ether, 4-hydroxymethyl biphenyl and the like.
The reaction between the phenolic hydroxyl group in the resin and the methylol compound is shown in the following formula.

In a preferred example of isocyanate, the compound (b) includes a compound represented by the above general formula (17), wherein R ₂₄ is a monovalent organic group having 1 to 12 carbon atoms. Such a compound is advantageous in that the addition reaction can be carried out efficiently.

As a reaction between a phenolic hydroxyl group and an isocyanate, a reaction that urethanizes by addition is considered. Examples of the isocyanate include ethyl isocyanate, phenyl isocyanate, t-butyl isocyanate, 2-methacryloyloxyethyl isocyanate and the like.
The reaction between the phenolic hydroxyl group in the resin and the isocyanate is shown in the following formula.

In a preferred example of the blocked isocyanate, the compound (b) includes a compound represented by the above general formula (18), wherein R ₂₅ and M ₆ are monovalent organic groups having 1 to 10 carbon atoms. Such a compound is advantageous in that the addition reaction can be carried out efficiently.

As the reaction of the blocked isocyanate, urethanization may be considered by removing the protecting group alcohol, oxime compound, pyrazole compound or the like to generate isocyanate and adding it to the phenolic hydroxyl group. Examples of the blocked isocyanate include Karenz MOI-BM (trade name, manufactured by Showa Denko), Karenz MOI-BP (trade name, manufactured by Showa Denko), [O- (1′-methylpropylideneamino) carboxyamino] benzene, [(3,5-dimethylpyrazolyl) carbonylamino] benzene and the like.
The reaction of the phenolic hydroxyl group in the resin with the blocked isocyanate is shown in the following formula.

In a preferred example of the sulfate ester, the compound (b) includes a compound represented by the general formula (19), wherein R ₂₆ and M ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms. Such a compound is advantageous in that a substitution reaction can be efficiently performed.

As a reaction between the phenolic hydroxyl group and the sulfate ester, a reaction in which an alkyl group is substituted and etherified can be considered. Examples of such sulfate esters include dimethyl sulfate, diethyl sulfate, diisopropyl sulfate, diallyl sulfate and the like.
The reaction between the phenolic hydroxyl group in the resin and the sulfate ester is shown in the following formula.

  Particularly preferably, the compound (b) is at least one selected from compounds represented by formulas (9) to (19).

  The amount of the compound (b) used is preferably 5 to 200 parts by mass, more preferably 7 to 150 parts by mass, and still more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the resin (a) having a phenolic hydroxyl group. It is. When the amount used is 5 parts by mass or more, it is advantageous in terms of enhancing the reactivity, and when it is 200 parts by mass or less, it is advantageous in that the stability of the composition is maintained.

[(C) Photosensitive compound]
By selecting the type of the (c) photosensitive compound to be contained in the photosensitive resin composition, the photosensitive resin composition of the present invention can be made positive or negative. When the photosensitive resin composition of the present invention is made positive, it is necessary to select a photoacid generator as the photosensitive compound (c). As the photoacid generator, a naphthoquinone diazide (NQD) compound (that is, a photoactive compound having an NQD structure) (hereinafter also referred to as “NQD compound”), an onium salt, a halogen-containing compound, etc. can be used. From the viewpoints of stability and storage stability, NQD compounds are preferred.

  Examples of the onium salt include iodonium salts, sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, and the like, and onium salts selected from the group consisting of diaryliodonium salts, triarylsulfonium salts, and trialkylsulfonium salts are preferable.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable from the viewpoint of increasing sensitivity.

  Examples of the naphthoquinone diazide compound include compounds having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure, and examples thereof include US Pat. No. 2,772,972, US Pat. No. 2,797. No. 213, U.S. Pat. No. 3,669,658, and the like. The naphthoquinonediazide structure includes 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound having a specific structure described in detail below, and 1,2-naphthoquinonediazide-5-sulfonic acid ester of the polyhydroxy compound. At least one NQD compound selected from the group consisting of:

  The NQD compound is obtained by subjecting a naphthoquinone diazide sulfonic acid compound to sulfonyl chloride with chlorosulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazide sulfonyl chloride to a polyhydroxy compound. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, tetrahydrofuran, etc. The NQD compound can be obtained by reacting in the presence of a basic catalyst for esterification, and washing the resulting product with water and drying.

｛式中、Ｑは、水素原子、又は下記式群：

のいずれかで表されるナフトキノンジアジドスルホン酸エステル基であるが、すべてのＱが同時に水素原子であることはない。｝ Examples of preferable NQD compounds include those represented by the following general formula group.

{Wherein Q is a hydrogen atom or the following group of formulas:

The naphthoquinone diazide sulfonate group represented by any of the above, but not all Q are hydrogen atoms at the same time. }

  Further, a naphthoquinone diazide sulfonyl ester compound containing a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule can be used, and a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be used. Can also be used in combination.

  When the photosensitive resin composition of the present invention is a positive type, the blending amount of the (c) photosensitive compound with respect to 100 parts by mass of the resin (a) having a phenolic hydroxyl group is preferably 1 to 50 parts by mass. 5 to 30 parts by mass is more preferable. (C) When the blending amount of the photosensitive compound is 1 part by mass or more, the patterning property of the resin is good, and when it is 50 parts by mass or less, the tensile elongation of the cured film is good, and There is little development residue (scum) in the exposed area.

  In addition, when using the photosensitive resin composition of this invention by a negative type, the compound which generate | occur | produces an acid by irradiation of actinic rays is used as (c) photosensitive compound, This is mentioned later and (d) Crosslinking agent By combining, it can be used as a negative type. Examples of compounds that generate an acid upon irradiation with actinic rays include the following compounds a) to k).

A) Trichloromethyl-s-triazines Tris (2,4,6-trichloromethyl) -s-triazine, 2-phenyl-bis (4,6-trichloromethyl) -s-triazine, 2- (3-chlorophenyl) -Bis (4,6-trichloromethyl) -s-triazine, 2- (2-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -bis (4 6-trichloromethyl) -s-triazine, 2- (3-methoxyphenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxyphenyl) -bis (4,6-trichloromethyl) ) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (3-methylthiophenyl) Bis (4,6-trichloromethyl-s-triazine, 2- (2-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -bis (4,6 -Trichloromethyl) -s-triazine, 2- (3-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (3,4,5-trimethoxy-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methylthio-β-styryl) -bis (4 , 6-Trichloromethyl) -s-triazine, 2- (3-methylthio-β-styryl) -bis (4,6-trichloromethyl) -s-triazine, 2- (2-methylthio-β Styryl) - bis (4,6-trichloromethyl) -s-triazine and the like;

A) Diaryl iodonium compounds diphenyl iodonium tetrafluoroborate, diphenyl iodonium tetrafluorophosphate, diphenyl iodonium tetrafluoroarsenate, diphenyl iodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, 4-methoxyphenyl Phenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4- Meto Xiphenylphenyliodonium-p-toluenesulfonate, bis (4-ter-butylphenyl) iodonium tetrafluoroborate, bis (4-ter-butylphenyl) iodonium hexafluoroarsenate, bis (4-ter-butylphenyl) iodonium Trifluoromethanesulfonate, bis (4-ter-butylphenyl) iodonium trifluoroacetate, bis (4-ter-butylphenyl) iodonium-p-toluenesulfonate, etc .;

C) Triarylsulfoniums Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfo NATO, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium tri Fluoroacetate, 4-methyl Toxiphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethane Sulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiophenyl diphenyl-p-toluene sulfonate and the like.

  Among these compounds, trichloromethyl-S-triazines include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-chlorophenyl) -bis (4, 6-trichloromethyl) -S-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -S-triazine, 2- (4-methoxy-β-styryl) -bis (4,6- Triphenylmethyl) -S-triazine, 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -S-triazine and the like, and diaryliodonium compounds include diphenyliodonium trifluoroacetate and diphenyliodonium trifluoromethane. Sulfonate, 4-methoxyphenylphenyliodonium trifluorometa Sulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, etc., and triarylsulfonium, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyl Suitable examples include diphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, and the like.

D) Diazoketone compound Examples of the diazoketone compound include 1,3-diketo-2-diazo compound, diazobenzoquinone compound, diazonaphthoquinone compound, and the like, and specific examples include 1,2-naphthoquinonediazide-4 of phenols. -A sulfonic acid ester compound can be mentioned.

E) Sulfone compounds Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds. Specific examples include 4-trisphenacylsulfone, mesitylphenacyl. Examples include sulfone and bis (phenacylsulfonyl) methane.

F) Sulfonic acid compound Examples of the sulfonic acid compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Preferred examples include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, o-nitrobenzyl p-toluene sulfonate, and the like.

G) Sulfonimide compound Specific examples of the sulfonimide compound include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N -(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide and the like can be mentioned.

C) Oxime ester compound 2- [2- (4-Methylphenylsulfonyloxyimino)]-2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (trade name “Ciba Specialty Chemicals”) Irgacure PAG121 "), [2- (propylsulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (for example, trade name" Irgacure PAG103 "by Ciba Specialty Chemicals), [2- (n-octanesulfonyloxyimino) -2,3-dihydrothiophene-3-ylidene] -2- (2-methylphenyl) acetonitrile (for example, trade name “Irgacure PAG108”, manufactured by Ciba Specialty Chemicals), α- ( n-octance Sulfonyl oxy) -4-methoxybenzyl cyanide (e.g. Ciba Specialty Chemicals tradename "CGI725"), and the like.

I) Diazomethane compounds Specific examples of the diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.

  In particular, from the viewpoint of sensitivity, the above) oxime ester compound group is particularly preferable.

  When the photosensitive resin composition of the present invention is a negative type, the blending amount of the (c) photosensitive compound with respect to 100 parts by mass of the resin (a) having a phenolic hydroxyl group is 0.1 to 100 parts by mass. Is preferable, and it is more preferable that it is 1-40 mass parts. If the blending amount is 0.1 parts by mass or more, a sensitivity improvement effect can be obtained satisfactorily. If the blending amount is 100 parts by mass or less, the mechanical properties of the cured film are good.

[(D) Crosslinking agent]
In the present invention, when (d) a crosslinking agent is used, when the coating film of the photosensitive resin composition of the present invention is heat-cured, film properties such as mechanical properties, heat resistance, and chemical resistance can be enhanced. . In order to enhance the membrane performance satisfactorily, (d) the cross-linking agent is preferably two or more —N— (CH ₂ —OR) groups, wherein R is a hydrogen atom or a carbon number of 1 to 4. Represents an alkyl group. }, Two or more —C— (CH ₂ —OR) groups {wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. }, A compound having two or more epoxy groups, a compound having two or more isocyanate groups, a compound obtained by reacting two or more isocyanate groups with an alcohol, oxime or pyrazole, two or more oxazolyls One or more compounds selected from the group consisting of a compound having a group and a compound having two or more unsaturated bonds. These compounds can be used alone or in admixture of two or more.

(D) Two or more —N— (CH ₂ —OR) groups in the crosslinking agent {wherein, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. }, For example, melamine resins and urea resins in which the N-position is substituted with a methylol group or an alkoxymethyl group are exemplified. Specifically, melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine resin, alkoxymethylated benzoguanamine resin, alkoxymethylated glycoluril resin, alkoxymethylated urea Examples thereof include resins. Among these, alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins are known methylolated melamine resins, methylolated benzoguanamine resins, and methylol groups of methylolated urea resins. Are each converted to an alkoxymethyl group.

  Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, and the like, but commercially available Cymel 300, 301, 303, 370, 325. 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR 65, 300 (manufactured by Mitsui Cytec Co., Ltd.), Nicarax MX-270, -280,- 290, Nicarak MS-11, Nicarak MW-30, -100, -300, -390, -750 (above, manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

(D) Two or more —C— (CH ₂ —OR) groups in the crosslinking agent {wherein, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. }, For example, 1,4-bis (methoxymethyl) benzene, 4,4′-biphenyldimethanol, 4,4′-bis (methoxymethyl) biphenyl, commercially available 26DMPC, 46DMOC, DM -BIPC-F, DM-BIOC-F, TM-BIP-A (above, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PC, DML-PCHP, DML -PTBP, DML-34X, DML-EP, DML-POP, DML-OC, dimethylol-Bis-C, dimethylol-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP , DML-MB25, DML-MTrisPC, DML-Bis25X-34XL, DML Bis25X-PCHP, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymer-p-cresol, TriML-P, TriML-35XL, TriML- TrisCR-HAP, HML-TPPHBA, HML-TPPHAP, HMOM-TPPHBA, and HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) are included.

  (D) Examples of the compound having two or more epoxy groups in the crosslinking agent include 1,1,2,2-tetra (p-hydroxyphenyl) ethanetetraglycidyl ether, glycerol triglycidyl ether, and ortho secondary butyl phenyl. Glycidyl ether, 1,6-bis (2,3-epoxypropoxy) naphthalene, diglycerol polyglycidyl ether, polyethylene glycol glycidyl ether, triglycidyl isocyanurate, Denacol EX-201, EX-313, EX-314, EX-321 , EX-411, EX-511, EX-512, EX-612, EX-614, EX-614B, EX-731, EX-810, EX-911, EM-150 (trade name, Nagase ChemteX Corporation Epoxy compounds such as It is below.

  (D) Compounds having two or more isocyanate groups in the crosslinking agent, and compounds obtained by reacting two or more isocyanate groups with alcohol, oxime or pyrazole include 4,4′-diphenylmethane diisocyanate and tolylene diisocyanate. Narate, 1,3-phenylene bismethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Takenate 500, 600, Cosmonate NBDI, ND (above, trade name, manufactured by Mitsui Chemicals), Duranate 17B-60PX, TPA-B80E, MF-B60X, MF-K60X, E402-B80T (above, trade name, manufactured by Asahi Kasei Chemical), BI-7642, BI-7950, BI-7981 (above, trade name, B xenden Co., Ltd.), Coronate AP-M, Millionate MS-50 (trade names, manufactured by Nippon Polyurethane Industry Co.), and the like.

  (D) Examples of the compound having two or more oxazolyl groups in the crosslinking agent include 2,2′-bis (2-oxazoline), 2,2′-isopropylidenebis (4-phenyl-2-oxazoline), 1 , 3-bis (4,5-dihydro-2-oxazolyl) benzene, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, Epocross K-2010E, K-2020E, K-2030E, WS- 500, WS-700, RPS-1005 (above, trade name, manufactured by Nippon Shokubai Co., Ltd.) and the like.

(D) As a compound having two or more unsaturated bonds in the crosslinking agent, vinyl acetate, trimethylolpropane trimethacrylate, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitic acid, tetraallyl pyromellitic acid Two or more of ester, pentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, BANI-M, BANI-X (above, trade name, manufactured by Maruzen Petrochemical Co., Ltd.) And compounds having an unsaturated bond.

(D) As a crosslinking agent, in addition to the above,
A compound having two or more oxetane groups; for example, xylylenebisoxetane, 3-ethyl-3 {[(3-ethyloxetane-yl) methoxy] methyl} oxetane,
Compounds having two or more carbodiimide groups; for example, carbodilite SV-02, V-01, V-02, V-03, V-04, V-05, V-07, V-09, E-01, E -02, LA-1 (above, trade name, manufactured by Nisshinbo Chemical Co., Ltd.)
Compound having aldehyde group or modified aldehyde; for example, formaldehyde, glutaraldehyde, hexamethylenetetramine, trioxane, glyoxal, malondialdehyde, succinaldehyde,
Metal chelating agents; for example, acetylacetone aluminum (III) salt, acetylacetone titanium (IV) salt, acetylacetone chromium (III) salt, acetylacetone magnesium (II) salt, acetylacetone nickel (II) salt, trifluoroacetylacetone aluminum (III) salt, Trifluoroacetylacetone titanium (IV) salt, trifluoroacetylacetone chromium (III) salt, trifluoroacetylacetone magnesium (II) salt, trifluoroacetylacetone nickel (II) salt,
Is mentioned.

  (D) The usage-amount of a crosslinking agent becomes like this. Preferably it is 1-60 mass parts with respect to 100 mass parts of (a) resin which has a phenolic hydroxyl group, More preferably, it is 3-50 mass parts. When the amount used is 1 part by mass or more, the crosslinking proceeds well, and the effect of enhancing the film properties can be obtained satisfactorily. On the other hand, if the amount used is 60 parts by mass or less, the elongation is kept good.

[Other ingredients]
If necessary, the photosensitive resin composition may contain additives such as a dye, a surfactant, an adhesion aid for improving adhesion to the substrate, a dissolution accelerator, and a crosslinking accelerator. is there.

  Examples of the dye include methyl violet, crystal violet, and malachite green. As a compounding quantity of dye, 0.1-30 mass parts is preferable with respect to 100 mass parts of (a) resin which has a phenolic hydroxyl group.

  Examples of the surfactant include non-ionic surfactants composed of polyglycols such as polypropylene glycol and polyoxyethylene lauryl ether or derivatives thereof, and Fluorard (registered trademark, trade name, manufactured by Sumitomo 3M), for example. Fluorosurfactants such as Megafac (registered trademark, trade name, manufactured by Dainippon Ink & Chemicals), Lumiflon (registered trademark, trade name, manufactured by Asahi Glass Co., Ltd.), such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) ), DBE (trade name, manufactured by Chisso Corporation), granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), and other organosiloxane surfactants. As a compounding quantity in the case of using surfactant, (a) 0.01-10 mass parts is preferable with respect to 100 mass parts of resin which has phenolic hydroxyl group.

  Examples of the adhesion assistant include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy silane, epoxy polymer, and various alkoxy silanes.

  Preferred examples of the alkoxysilane include, for example, tetraalkoxysilane, bis (trialkoxysilyl) methane, bis (trialkoxysilyl) ethane, bis (trialkoxysilyl) ethylene, bis (trialkoxysilyl) hexane, and bis (trialkoxy). Silyl) octane, bis (trialkoxysilyl) octadiene, bis [3- (trialkoxysilyl) propyl] disulfide, N-phenyl-3-aminopropyltrialkoxysilane, 3-mercaptopropyltrialkoxysilane, 2- (trialkoxy) Silylethyl) pyridine, 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, vinyltrialkoxysilane, 3-ureidopropyltrialkoxysila , 3-isocyanatopropyltrialkoxysilane, 3- (trialkoxysilyl) propyl succinic anhydride, N- (3-trialkoxysilylpropyl) -4,5-dihydroimidazole, 2- (3,4-epoxycyclohexyl) Ethyl trialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-aminopropyltrialkoxysilane and 3-aminopropyl dialkoxyalkylsilane and acid anhydride or acid dianhydride And a product obtained by converting the amino group of 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane into a urethane group or a urea group. In addition, examples of the alkyl group in the above compound include a methyl group, an ethyl group, a propyl group, and a butyl group, and examples of the acid anhydride include maleic acid anhydride, phthalic acid anhydride, 5-norbornene-2,3- Examples of the acid dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, and 4,4′-oxydiphthalic dianhydride. Examples of the urethane group include a t-butoxycarbonylamino group, and examples of the urea group include a phenylaminocarbonylamino group.

  As a compounding quantity in the case of using an adhesion support agent, 0.1-30 mass parts is preferable with respect to 100 mass parts of (a) resin which has a phenolic hydroxyl group.

  As the dissolution accelerator, a compound having a hydroxyl group or a carboxyl group is preferable. Examples of the compound having a hydroxyl group include the ballast agent used in the above-mentioned naphthoquinone diazide compound, paracumylphenol, bisphenols, resorcinol, and linear phenol compounds such as MtrisPC and MtetraPC, TrisP-HAP, TrisP -Non-linear phenolic compounds such as PHBA and TrisP-PA (all manufactured by Honshu Chemical Industry Co., Ltd.), 2 to 5 phenol substitutes of diphenylmethane, 1 to 5 phenol substitutes of 3,3-diphenylpropane, One-to-two reactant of 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane and 5-norbornene-2,3-dicarboxylic anhydride, bis- (3-amino-4-hydroxy Phenyl) sulfone and 1,2-cyclohexyldicarboxylic anhydride 1: 2 reaction product of, N- hydroxysuccinimide, N- hydroxy phthalimide, and the like N- hydroxy 5-norbornene-2,3-dicarboxylic acid imide.

  Examples of the compound having a carboxyl group include 3-phenyl lactic acid, 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2. -(1-Naphthyl) propionic acid, mandelic acid, atrolactic acid, acetylmandelic acid, α-methoxyphenylacetic acid, 3-phenyllactic acid, 4-hydroxyphenyllactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid 4-hydroxy-3-methoxymandelic acid, 2-methoxy-2- (1-naphthyl) propionic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxy Examples thereof include mandelic acid, mandelic acid, atrolactic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid, O-acetylmandelic acid, α-methoxyphenylacetic acid and the like.

  As a compounding quantity when using a solubility promoter, 0.1-30 mass parts is preferable with respect to 100 mass parts of (a) resin which has a phenolic hydroxyl group.

  As the crosslinking accelerator, those that generate an acid, a base, or a radical by heat or light are preferable. Examples of those that generate acid by heat or light include TPS-105, 1000, DTS-105, NDS-105, 165 (trade name, manufactured by Midori Chemical Co., Ltd.), DPI-DMAS, TTBPS-TF, TPS-TF, DTBPI. Onium salts such as -TF (trade name, manufactured by Toyo Gosei Co., Ltd.), sulfonic acid esters such as methyl methanesulfonate, ethyl methanesulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methoxyethyl p-toluenesulfonate , NAI-100, 101, 105, 106, PAI-101 (trade name, manufactured by Midori Chemical Co., Ltd.), Irgacure PAG-103, 108, 121, 203, CGI-1380, 725, NIT, 1907, PNBT (trade name, And oxime sulfonates such as BASF Japan).U-CATSA-1, 102, 506, 603, 810 (trade name, manufactured by San Apro), CGI-1237, 1290, 1293 (trade name, manufactured by BASF Japan) are those that generate bases by heat or light. Such as amine salts such as 2,6-piperidine or butylamine, diethylamine, dibutylamine, N, N'-diethyl-1,6-diaminohexane, hexamethylenediamine, etc. converted to urethane groups or urea groups, etc. Is mentioned. Examples of the urethane group include a t-butoxycarbonylamino group, and examples of the urea group include a phenylaminocarbonylamino group. Examples of radicals generated by heat or light include alkylphenones such as Irgacure 651, 184, 2959, 127, 907, 369, 379 (trade name, manufactured by BASF Japan), Irgacure 819 (trade name, manufactured by BASF Japan). ), Etc., titanocene such as Irgacure 784 (trade name, manufactured by BASF Japan), and oxime ester such as Irgacure OXE01, 02 (trade name, manufactured by BASF Japan).

<Method for forming cured relief pattern>
Another aspect of the present invention includes a step of applying the above-described photosensitive resin composition of the present invention to a substrate, a step of exposing the photosensitive resin composition, and developing the photosensitive resin composition after the exposure. Provided is a method for producing a cured relief pattern, comprising a step of forming a relief pattern, and a step of heating the relief pattern to form a cured relief pattern. The photosensitive resin composition of the present invention is preferably used for forming a semiconductor protective film or an interlayer insulating film. An example of this method will be described below.

  First, the photosensitive resin composition of the present invention is applied to a suitable support or substrate such as a silicon wafer, ceramic, aluminum substrate or the like. At this time, in order to ensure the water-resistant adhesion between the pattern to be formed and the support, an adhesion assistant such as a silane coupling agent may be applied to the support or the substrate in advance. The photosensitive resin composition is applied by spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, or the like. Next, after prebaking at 80-140 degreeC and drying the coating film of the photosensitive resin composition, the photosensitive resin composition is exposed. As the actinic radiation for exposure, 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. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably g-line, h-line or i-line of a mercury lamp, and may be used alone or in combination with two or more actinic rays. As the exposure apparatus, a contact aligner, a mirror projection, and a stepper are particularly preferable.

  Next, development can be performed by selecting from methods such as dipping, paddle, and rotary spraying. By development, an exposed portion (in the case of a positive type) or an unexposed portion (in the case of a negative type) can be eluted and removed from the applied photosensitive resin composition to obtain a relief pattern. Developers include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. An aqueous solution such as a quaternary ammonium salt such as quaternary ammonium 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 may be used. In these, the tetramethylammonium hydroxide aqueous solution is preferable, The density | concentration of this tetramethylammonium hydroxide becomes like this. Preferably, it is 0.5-10 mass%, More preferably, it is 1-5 mass%.

  After development, the pattern film can be obtained by washing with a rinse solution and removing the developer. As a rinse liquid, distilled water, methanol, ethanol, isopropanol, etc. can be used individually or in combination of 2 or more types.

  Finally, a cured relief pattern can be obtained by heating the relief pattern thus obtained. The heating temperature is preferably 150 ° C. or higher and 280 ° C. or lower.

  In the method of forming a cured relief pattern using a commonly used polyimide or polybenzoxazole precursor composition, the polyimide or polybenzoxazole is heated by heating to 300 ° C. or higher to advance a dehydration cyclization reaction. However, in the method for producing a cured relief pattern of the present invention, there is no need for this, so that it can be suitably used for a semiconductor device that is vulnerable to heat. For example, it is suitably used for a semiconductor device having an insulating layer made of a high-dielectric material or a ferroelectric material having a process temperature restriction, such as an oxide of a refractory metal such as titanium, tantalum, or hafnium. .

  Of course, if the semiconductor device does not have such heat resistance restrictions, heat treatment may be performed at 300 to 400 ° C. also in this method. Such heat treatment can be performed by using a hot plate, an oven, or a temperature rising oven in which a temperature program can be set. Air may be used as the atmospheric gas when performing the heat treatment, and an inert gas such as nitrogen or argon may be used. Further, when it is necessary to perform heat treatment at a lower temperature, heating may be performed under reduced pressure using a vacuum pump or the like.

<Semiconductor device>
A semiconductor device having a cured relief pattern manufactured by the above-described method using the photosensitive resin composition of the present invention is also an embodiment of the present invention. The semiconductor device of the present invention has the above-described cured relief pattern as, for example, a surface protective film, an interlayer insulating film, a rewiring insulating film, a flip chip device protective film, or a protective film of a device having a bump structure. The semiconductor device of the present invention can be manufactured by combining a known method for manufacturing a semiconductor device and the above-described method for manufacturing a cured relief pattern of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all by these Examples. In addition, unless otherwise indicated, the part in a following example and a comparative example is used by the meaning of a mass part. Moreover, about each characteristic of hardened | cured material, it evaluated in the following way.

<Measurement of OH modification rate by IR>
(A) a gamma butyrolactone solution containing only a resin having a phenolic hydroxyl group (referred to as “solution-1”), and a gamma butyrolactone solution (“solution-”) of a mixture of a resin having a phenolic hydroxyl group and (b) a compound. 2)) was prepared. Two barium fluoride plates (20 mm diameter and 2 mm thickness) are prepared, each of Solution-1 and Solution-2 is applied, and heated and dried on a hot plate at 90 ° C. for 180 seconds to obtain a range of 1 to 5 μm. The coating film was produced so that it might become thickness. First, using a Fourier transform infrared spectrometer, the spectrum is measured by a transmission method in dry air, and the absorbance of a peak corresponding to OH stretching vibration of 3,000 to 4,000 cm ⁻¹ of the spectrum is measured from the baseline. It calculated | required as the distance to a peak top (it was set to C about the coating film from the solution-2 from the coating film from the solution-1). Incidentally, when measuring the absorbance of the peak, the baseline is a straight line connecting two points of 4,000 cm ^-1 and 2,000 cm ^-1, it had been confirmed that there is no such undulation. Next, this sample was heated at 250 ° C. for 1 hour under a nitrogen stream in a curing furnace (manufactured by Koyo Thermo Systems Co., Ltd.). The sample after heating is again subjected to spectrum measurement by a transmission method in a dry air using a Fourier transform infrared spectrometer, and the absorbance of the peak corresponding to the OH stretching vibration of 3,000 to 4,000 cm ⁻¹ of the spectrum. Was determined in the same manner as A and C (B for the coating film from solution-1 and D for the coating film from solution-2).
As the hydroxyl group modification rate E, the intensity decrease degree of the OH group absorbance was determined by the following formula.
E = (C−D) / C− (A−B) / A

<Change in residual stress due to the presence or absence of moisture in the environment (change in warpage)>
For a 6-inch silicon wafer, the amount of warpage was measured with a thin film stress measuring device KLA-Tencor FLX-2300 (initial value).

  Next, a substrate with a cured film is obtained. In the case of a positive type, a photosensitive resin composition is spin-coated, heated at 120 ° C. for 3 minutes using a hot plate, and a uniform coating film having a thickness of 10 μm. Was made. Then, it heated at 200 degreeC under nitrogen stream for 1 hour in the curing furnace, and obtained the board | substrate with a cured film.

In the case of the negative type, the photosensitive resin composition was spin-coated and heated at 100 ° C. for 3 minutes using a hot plate to prepare a uniform coating film having a thickness of 10 μm. Thereafter, using an aligner (PLA manufactured by Canon Inc.), the ultraviolet light from the high pressure mercury lamp was exposed so that the exposure amount at a wavelength of 365 nm was 3,000 to 6,000 J / m ² . Subsequently, it heated at 110 degreeC with the hotplate for 3 minutes (PEB). This was heated in a curing furnace at 200 ° C. under a nitrogen stream for 1 hour to obtain a substrate with a cured film.

  About the obtained board | substrate with a cured film, the change of the curvature amount by the presence or absence of the water | moisture content in an environment was measured with the thin film stress measuring device KLA-Tencor FLX-2300, and the residual stress was calculated | required.

  The measurement of the amount of warp due to the presence or absence of moisture in the environment was performed according to the following procedure. First, the silicon wafer was placed on a measuring table, the amount of warpage was measured under air at 25 ° C. and humidity of 50%, and the residual stress was calculated taking the initial value into account (under-air stress). Next, a nitrogen stream was passed through the measurement table, and after 10 minutes, the amount of warpage of the silicon wafer was measured again, and the residual stress was calculated taking into account the initial value (under-nitrogen stress). The change in stress was determined by subtracting the value of stress under air from the value of stress under nitrogen.

<Chemical resistance to alkaline chemicals>
The photosensitive resin composition was spin-coated on a 6-inch silicon wafer with a spin coater (Daishin Screen Manufacturing Co., Ltd .: Dspin, trade name), pre-baked on a hot plate at 120 ° C. for 180 seconds, and a film thickness of about 10 μm. The coating film was formed. The film thickness was measured with a film thickness measuring device (Dainippon Screen Mfg. Co., Ltd .: Lambda Ace). This coating film is exposed using a stepper (Nikon Corporation: NSR2005i8A) having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern, and this is exposed to an alkali developer (Clariant Japan, AZ300MIF developer, 2 .38 mass% tetramethylammonium hydroxide aqueous solution), development was performed at 23 ° C., and rinsed with pure water to form a relief pattern. Thereafter, the substrate was heated in a curing furnace at 200 ° C. for 1 hour under a nitrogen stream to obtain a substrate with a cured pattern film. This was applied to PRS-3000 (resist stripper containing 1-amino-2-propanol, N-methylpyrrolidone, tetrahydrothiophene 1,1-dioxide as a main component, manufactured by JT Baker) at 50 ° C. for 30 minutes. After immersion, rinse with water, observe the cured pattern after immersing the resist stripping solution using an optical microscope. If there is no change from before immersion, the relief pattern peels off the substrate or cracks occur, etc. If the damage was correct, it was marked as x.

[Reference Example 1]
<Synthesis of polybenzoxazole precursor a-2)>
In a 2 L separable flask, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane and 75.9 g of pyridine.
(0.96 mol) and 692 g of DMAc were mixed and stirred at room temperature (25 ° C.) to dissolve. Separately, a mixed solution in which 19.7 g (0.12 mol) of 5-norbornene-2,3-dicarboxylic anhydride was dissolved in 88 g of DMDG was added dropwise from the dropping funnel to the obtained mixture. The time required for the dropwise addition was 40 minutes, and the maximum reaction solution temperature was 28 ° C.

After completion of the dropwise addition, the flask was heated to 50 ° C. with a hot water bath and stirred for 18 hours, and then the IR spectrum of the reaction solution was measured. The characteristic absorption of imide groups at 1385 cm ⁻¹ and 1772 cm ⁻¹ appeared. confirmed.

  Next, the flask was cooled to 8 ° C. with a water bath, and separately, a mixed solution in which 142.3 g (0.48 mol) of 4,4′-diphenyl ether dicarboxylic acid dichloride was dissolved in 398 g of DMDG was dropped from a dropping funnel. The time required for the dropping was 80 minutes, and the maximum reaction solution temperature was 12 ° C. Three hours after the completion of dropping, the reaction solution was dropped into 12 l of water under high-speed stirring to disperse and precipitate the polymer. The purified precipitate was collected, washed with water as appropriate, dehydrated and then vacuum dried to obtain a polybenzoxazole precursor (a-2). The weight average molecular weight of the thus synthesized polybenzoxazole precursor by gel permeation chromatography (GPC) was 14,000 in terms of polystyrene.

[Reference Example 2]
<Synthesis of soluble polyimide (a-4)>
In a separable flask having a volume of 2 L, 197.8 g (0.54 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, N-methyl-2-pyrrolidone (hereinafter referred to as “NMP”) 600 g) was added. After stirring and dissolving at room temperature, 164.4 g (0.53 mol) of bis (3,4-dicarboxyphenyl) ether dianhydride was charged. After stirring at 120 ° C. for 5 hours under nitrogen, the temperature was raised to 180 ° C. and dehydration reaction was performed for 5 hours. After completion of the reaction, the reaction mixture was poured into water, and the product was reprecipitated, filtered, and vacuum dried to obtain 206 g of a polymer (soluble polyimide (a-4)). The weight average molecular weight by GPC of the obtained polymer was 15,000 in terms of polystyrene.

[Reference Example 3]
<Synthesis of phenol resin (a-5)>
Pyrogallol 50.4 g (0.4 mol), 4,4′-bis (methoxymethyl) biphenyl 72.7 g (0.3 mol), diethyl sulfate in a separable flask with a Dean-Stark device of 0.5 liter capacity 2.1 g (0.15 mol) and 27 g of DMDG were mixed and stirred at 70 ° C. to dissolve the solid matter.

  The mixed solution was heated to 120 ° C. with an oil bath, and generation of methanol was confirmed from the reaction solution. The reaction solution was stirred at 120 ° C. for 2 hours.

  Next, the reaction vessel was cooled in the atmosphere, and 100 g of tetrahydrofuran was separately added thereto and stirred. The reaction diluted solution is dropped into 4 L of water under high-speed stirring to disperse and precipitate the resin, which is recovered, appropriately washed with water, dehydrated and then vacuum-dried, and the above general formula (9):

A biphenyldiyltrihydroxybenzene resin having a structure represented by the formula: The weight average molecular weight by GPC of the resin thus synthesized was 11,000 in terms of polystyrene.

[Examples 1 to 13, Comparative Examples 1 to 4]
As shown in Table 1, (a) a resin having a phenolic hydroxyl group, a compound selected from a-1 to a-5 described later, and (b) a compound selected from b-1 to b-4 described later as a compound. (C) a compound selected from c-1 to c-2 described later as a photosensitive compound, (d) a combination of compounds selected from d-1 to d-6 described later as a crosslinking agent, and a silane coupling agent 2 A part by mass was dissolved in 120 parts by mass of gamma-butyrolactone as a solvent. The properties of this composition were measured according to the evaluation method. The results are shown in Table 2.

a-1: EP-4080G (Cresol novolak resin manufactured by Asahi Organic Materials Industries)
a-2: Polybenzoxazole precursor synthesized in Reference Example 1 a-3: Poly (p-hydroxystyrene) (Maruka Linker M manufactured by Maruzen Petrochemical Co., Ltd.)
a-4: soluble polyimide synthesized in Reference Example 2 a-5: phenolic resin synthesized in Reference Example 3 b-1: linalool (alcohol)
b-2: Amyl acetoacetate (carboxylic acid ester)
b-3: Diphenyl carbonate (carbonate ester)
b-4: Cyclohexyl isocyanate (isocyanate)
c-1: TS-425 (see below)
c-2: PAG-121 (Ciba Specialty Chemical)
d-1: Hexamethoxymethylmelamine (compound having two or more —N— (CH ₂ —OR) groups, Nikalac MW-390 manufactured by Sanwa Chemical Co., Ltd.)
d-2: Duranate TPA-B80X (a compound obtained by reacting two or more isocyanate groups with an oxime, manufactured by Asahi Kasei Chemicals Corporation)
d-3: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene (compound having two or more oxazolyl groups)
d-4: 4,4′-bis (methoxymethyl) biphenyl (compound having two or more —C— (CH ₂ —OR) groups)
d-5: Triallyl trimellitic acid (compound having two or more unsaturated bonds)
d-6: triglycidyl isocyanurate (compound having two or more epoxy groups)
Solvent: Gamma butyrolactone silane coupling agent: Compound in which amino group of 3-aminopropyltriethoxysilane is converted to urethane group

｛式中、Ｑの内８３％が下記構造：

で表される構造であり、残余が水素原子である。｝ The photosensitive compound (c-1)
Photoacid generator represented by the following general formula

{In the formula, 83% of Q has the following structure:

The remainder is a hydrogen atom. }

  As shown in Table 2, a substrate with a cured film obtained from a composition containing a compound that reacts with (b) a phenolic hydroxyl group has a small change in stress, and (b) a compound that reacts with a phenolic hydroxyl group (D) The relief pattern obtained from the composition containing both of the crosslinking agents was excellent in chemical resistance against alkaline chemicals.

  ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which provides the cured film for semiconductor protective films, such as a surface protective film excellent in the change of a residual stress and chemical resistance, and an interlayer insulation film, can be provided.

Claims (22)

(A) a resin having a phenolic hydroxyl group,
(B) a compound having only one group that reacts with the phenolic hydroxyl group of the resin (a) and satisfying the following formula (1):
(C) a photosensitive compound, and (d) a crosslinking agent,
A photosensitive resin composition comprising:
0.2 ≦ (C−D) / C− (A−B) / A ≦ 1 (1)
(In the formula, A, B, C, and D are normalized peak intensities corresponding to OH stretching vibrations at 3,000 to 4,000 cm ⁻¹ of the infrared absorption spectrum, respectively, and A is (a) The peak intensity measured only with B, B is the peak intensity measured only after heating in an inert gas atmosphere at 250 ° C. for 1 hour, and C is the peak measured with the mixture of (a) and (b). Intensity, D indicates the peak intensity measured after heating at 250 ° C. for 1 hour in an inert gas atmosphere for the mixture of (a) and (b), respectively.   The photosensitive resin composition of Claim 1 whose said (a) resin which has a phenolic hydroxyl group is a phenol resin. The (d) crosslinking agent is two or more —N— (CH ₂ —OR) groups (wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). }, Two or more —C— (CH ₂ —OR) groups {wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. }, A compound having two or more epoxy groups, a compound having two or more isocyanate groups, a compound obtained by reacting two or more isocyanate groups with an alcohol, oxime or pyrazole, two or more oxazolyls The photosensitive resin composition according to claim 1 or 2, which is one or more compounds selected from the group consisting of a compound having a group and a compound having two or more unsaturated bonds.   The photosensitive resin composition of any one of Claims 1-3 which is an object for semiconductor protective film formation or interlayer insulation film formation. The resin (a) having a phenolic hydroxyl group is represented by the following general formula (2):

{In the formula, R ₂ represents a halogen atom; a nitro group; a cyano group; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; 6-20 aromatic groups; or the following general formula group (3):

(In the formula, R _3, R ₄ and R ₅ are each independently a hydrogen atom; an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms, and R ₆ is an aliphatic group having 1 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms. Or an aromatic group having 6 to 20 carbon atoms; a group represented by any one of
Y represents an aliphatic group having 2 to 10 carbon atoms which may have an unsaturated bond; an alicyclic group having 3 to 20 carbon atoms; an ethylene oxide group having an integer of 1 to 20 repeating units; or aromatic An organic group having a group;
However, in R ₂ , R ₃ , R ₄ , R _5, R ₆ and Y, the hydrogen atom may be substituted with at least one selected from the group consisting of a halogen atom, a carboxyl group, a nitro group and a cyano group. ,
a is an integer of 1-1000,
n is an integer of 1 to 3, and q is an integer of 0 to 3. }
The photosensitive resin composition of any one of Claims 1-4 which is a phenol resin which has a repeating structure represented by these. Y in the general formula (2) is the following general formula (4):

{Wherein, R _{7 to} R ₁₀ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine. }
Or a group represented by the following general formula (5):

{Wherein, R _{11 to} R ₁₄ each independently represents a hydrogen atom; or an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; Z represents a single bond; substituted with fluorine; An aliphatic group having 1 to 10 carbon atoms; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; an ethylene oxide group having 1 to 20 repeating units; or the following formula group (6):

A group represented by any one of the following: }
The photosensitive resin composition of Claim 5 which is group represented by these. Y in the general formula (2) is the following general formula (7):

{Wherein W is a single bond; an aliphatic group having 1 to 10 carbon atoms which may be substituted with fluorine; an alicyclic group having 3 to 20 carbon atoms which may be substituted with fluorine; 20 ethylene oxide groups; or the following formula group (8):

A group represented by any one of the following: }
The photosensitive resin composition of Claim 6 which is group represented by these. The compound (b) is represented by the following general formulas (9) to (19):

{In the formula, R _{15 to} R ₂₆ and M _{1 to} M ₇ each independently represent a monovalent organic group, and X represents a halogen atom. }
The photosensitive resin composition of any one of Claims 1-7 which is 1 or more types of compounds chosen from the group which consists of. The photosensitive resin composition according to claim 8, wherein the compound (b) has 1 to 20 carbon atoms of R _{15 to} R ₂₆ in the general formulas (9) to (19). Wherein (b) compounds, wherein is represented by the general formula (9), R ₁₅ is 3 to 15 carbon atoms, comprising a compound which is a monovalent aliphatic group having an unsaturated group, according to claim 8 Photosensitive resin composition. The compound in which the compound (b) is represented by the general formula (10), and R ₁₆ is a monovalent aliphatic group having 1 to 10 carbon atoms having a hydroxyl group or an aliphatic group having 1 to 10 carbon atoms. The photosensitive resin composition of Claim 8 containing. The compound (b) is represented by the general formula (11), R ₁₇ is a monovalent organic group having 2 to 15 carbon atoms, and M ₁ is a monovalent organic group having 2 to 15 carbon atoms. The photosensitive resin composition of Claim 8 containing a certain compound. The photosensitive compound according to claim 8, wherein the compound (b) comprises a compound represented by the general formula (12), wherein R ₁₈ and M ₂ are each independently a monovalent organic group having 1 to 10 carbon atoms. Resin composition. Wherein (b) compound is represented by the general formula (13), R ₁₉ is a monovalent organic group having 1 to 10 carbon atoms, X comprises chlorine, bromine or compound iodine, claims 8 The photosensitive resin composition as described in 2. The photosensitive compound according to claim 8, wherein the compound (b) includes a compound represented by the general formula (14), wherein R ₂₀ and M ₃ are each independently a monovalent organic group having 1 to 10 carbon atoms. Resin composition. The compound (b) is represented by the general formula (15), R ₂₁ is a monovalent organic group having 1 to 10 carbon atoms, and R ₂₂ is hydrogen or a monovalent organic group having 1 to 10 carbon atoms. The photosensitive resin composition according to claim 8, comprising a compound wherein M ₄ is hydrogen or a monovalent organic group having 1 to 5 carbon atoms. The compound (b) is represented by the general formula (16), R ₂₃ is a monovalent aromatic group having 6 to 15 carbon atoms, M ₅ is hydrogen or a monovalent organic compound having 1 to 10 carbon atoms. The photosensitive resin composition of Claim 8 containing the compound which is group. The photosensitive resin composition according to claim 8, wherein the compound (b) includes a compound represented by the general formula (17), wherein R ₂₄ is a monovalent organic group having 1 to 12 carbon atoms. The photosensitive compound according to claim 8, wherein the compound (b) includes a compound represented by the general formula (18), wherein R ₂₅ and M ₆ are each independently a monovalent organic group having 1 to 10 carbon atoms. Resin composition. The photosensitive compound according to claim 8, wherein the compound (b) comprises a compound represented by the general formula (19), wherein R ₂₆ and M ₇ are each independently a monovalent organic group having 1 to 10 carbon atoms. Resin composition. The process of apply | coating the photosensitive resin composition of any one of Claims 1-20 to a board | substrate,
Exposing the photosensitive resin composition;
A method for producing a cured relief pattern, comprising: developing a photosensitive resin composition after the exposure to form a relief pattern; and heating the relief pattern to form a cured relief pattern.   A semiconductor device comprising a cured relief pattern obtained by the method for producing a cured relief pattern according to claim 21.