JP2008224984A - Photosensitive resin composition, method for producing patterned cured film using the same and electronic component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which makes physical properties of a film after curing comparable favorably with those of a film cured at a high temperature, a method for producing a patterned cured film using the resin composition and electronic components. <P>SOLUTION: The resin composition contains (a) a polybenzoxazole precursor having a repeating unit represented by general formula (I) (wherein U or V denotes a divalent organic group and at least one of U and V is a group including a 1-30C aliphatic chain structure), (b) a photosensitizing agent and (c) a solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a positive-type photosensitive resin composition excellent in heat resistance containing a polybenzoxazole precursor, a method for producing a patterned cured film using the resin composition, and an electronic component, and in particular, sensitivity, resolution, development. The present invention relates to a positive photosensitive resin composition that is excellent in adhesion, heat resistance and chemical resistance at the time, and can obtain a pattern with a good shape, a method for producing a cured pattern film using the resin composition, and an electronic component .

  Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a surface protective film and an interlayer insulating film of a semiconductor element. This polyimide resin film is generally made by reacting tetracarboxylic dianhydride and diamine in a polar solvent at room temperature and normal pressure, and thinning a polyimide precursor (polyamic acid) solution (so-called varnish) by spin coating or the like. It is formed by dehydration ring closure (curing) (see, for example, Non-Patent Document 1).

  In recent years, a photosensitive polyimide obtained by imparting photosensitive characteristics to a polyimide resin itself has been used. When this photosensitive polyimide is used, the pattern forming process can be simplified, and a complicated pattern manufacturing process can be shortened (for example, see Patent Documents 1 to 3).

  Conventionally, an organic solvent such as N-methylpyrrolidone has been used for developing the photosensitive polyimide. Recently, however, there has been a proposal of a positive photosensitive resin that can be developed with an aqueous alkaline solution from the viewpoint of environment and cost. Has been made. As a method for obtaining such an alkali-developable positive photosensitive resin, a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (for example, see Non-Patent Document 2), soluble hydroxylimide or There is a method of mixing a naphthoquinone diazide compound with a polybenzoxazole precursor (for example, see Patent Documents 4 and 5). A resin obtained by such a method can be expected to have a low dielectric constant, and photosensitive polybenzoxazole is attracting attention together with photosensitive polyimide from such a viewpoint.

  Recently, a low temperature process has been desired as a process for forming a cured resin film such as an interlayer insulating film layer or a surface protective film layer of an electronic component. To cope with this, dehydration and ring closure can be performed at a low temperature. Polyimides and polybenzoxazoles have become indispensable because the properties of the membrane after ring closure are comparable to those obtained by dehydration and ring closure at high temperatures. However, when a polyimide precursor or polybenzoxazole precursor is thermally dehydrated and closed to form a polyimide thin film or polybenzoxazole thin film, a high temperature of about 350 ° C. is usually required. This high temperature around 350 ° C. may adversely affect the substrate. Therefore, recently, in order to avoid defects derived from the thermal history, it is desired to lower the processing temperature in the semiconductor manufacturing process. In order to achieve a lower processing temperature in this process, the surface protective film can be dehydrated and closed at a temperature lower than about 250 ° C. instead of the conventional high temperature around 350 ° C. A polyimide material or a polybenzoxazole material, whose physical properties are comparable to those obtained by dehydration and ring closure at high temperatures, is indispensable. However, in the case where dehydration and ring closure is performed by lowering the temperature using a thermal diffusion furnace, the physical properties of the membrane generally decrease.

  Here, it is generally known that the dehydration ring closure temperature of the polybenzoxazole precursor is higher than the dehydration ring closure temperature of the polyimide precursor (for example, J. Photopolym. Sci. Technol., Vol. 17, 207-213). Therefore, it is more difficult to dehydrate and cyclize the polybenzoxazole precursor at a temperature lower than 250 ° C. than to dehydrate and cyclize the polyimide precursor.

Japanese Patent Laid-Open No. 49-11541 JP 59-108031 A JP 59-219330 A Japanese Examined Patent Publication No. 64-60630 U.S. Pat. No. 4,395,482 Japanese Patent No. 2587148 Japanese Patent No. 3031434 US Pat. No. 5,739,915 Japan Polyimide Study Group "Latest Polyimides-Fundamentals and Applications" (2002) J. et al. Macromol. Sci. , Chem. , Vol. A24, 1407 (1987) Tetrahedron, vol. 57, 9225-9283 (2001)

  Photosensitive polyimide or photosensitive polybenzoxazole is usually cured at a high temperature around 350 ° C. after pattern formation. On the other hand, MRAM (Magnet Resistive RAM), which has recently emerged as a promising next-generation memory, is vulnerable to high-temperature processes, and low-temperature processes are desired. Therefore, even a buffer coat (surface protective film) material can be cured at a low temperature of about 280 ° C. or lower, not at a conventional high temperature of around 350 ° C., and the physical properties of the cured film are cured at a high temperature. Buffer coating materials that can provide incomparable performance have become essential. However, there has been a problem that a buffer coating material that can be cured at such a low temperature and that has performance comparable to that cured at a high temperature has not yet been obtained.

  The present invention has been made to solve the above-mentioned conventional problems, and the problem is to provide a polybenzoxazole photosensitive resin film having a specific structural unit having a high dehydration ring closure rate even at 280 ° C. or lower. By using a base resin, a photosensitive resin composition in which the physical properties of a cured film are comparable to those cured at high temperatures, a method for producing a patterned cured film using the resin composition, and an electronic component It is to provide.

  In order to solve the above problems, the photosensitive resin composition according to the present invention has a photosensitive polybenzoxazole precursor capable of alkali development as a base polymer, and the photosensitive polybenzoxazole is shown below. In the general formula (I) or (V), both or one of U and V has an aliphatic chain structure. With this structure, the polybenzoxazole precursor has a high dehydration ring closure rate even at about 280 ° C. or less, so that the use of this resin composition does not cause a difference from the physical properties of the cured film at high temperatures even at low temperature curing processes. A cured film rich in heat resistance can be obtained.

Moreover, even if this polybenzoxazole cured film having an aliphatic chain structure is formed by a curing process at a lower temperature, it exhibits high elongation at break, low dielectric constant, and excellent chemical resistance. The present invention can be developed with an alkaline aqueous solution by using the photosensitive resin composition, and the polybenzoxazole precursor having an aliphatic chain structure has high light transmittance, and thus has excellent sensitivity and resolution. The present invention provides a method for producing a patterned cured film, which can obtain a patterned cured film having a good shape and excellent heat resistance by the following low-temperature curing process.
Furthermore, the present invention uses a photosensitive resin composition that has a pattern of good shape and characteristics, and that can be cured by a low-temperature process. Provide high yield.

  That is, the photosensitive resin composition for low-temperature curing according to the present invention comprises (a) the general formula (I):

（式中、Ｕ又はＶは２価の有機基を示し、Ｕ又はＶの少なくとも一方が炭素数１〜３０の脂肪族鎖状構造を含む基である。）で示される繰り返し単位を有するポリベンゾオキサゾール前駆体と、（ｂ）感光剤と、及び（ｃ）溶剤とを含有してなることを特徴とする。

(In the formula, U or V represents a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms.) It comprises an oxazole precursor, (b) a photosensitizer, and (c) a solvent.

  In the photosensitive resin composition according to the present invention, at least one of U or V in the general formula (I) of the component (a) is represented by the following general formula (UV1):

（式中、Ｒ¹、Ｒ²は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、aは１〜３０の整数を示す。）で表される構造を含む基、または下記に示す一般式（ＵＶ２）：

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30), or a group having the structure General formula (UV2):

（式中、Ｒ³〜Ｒ⁸は、各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、aからｃは各々独立に１〜６の整数を表し、ｄは０〜３の整数である。また、式中Ａは−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂、−Ｃ≡Ｃ−、−Ｒ⁹Ｃ＝ＣＲ¹⁰−である。Ｒ⁹〜Ｒ¹⁰は、各々独立に水素、フッ素又は炭素数１〜６のアルキル基。）で表される構造を含む基、であることを特徴とする。

(Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, a to c each independently represents an integer of 1 to 6, and d is 0 to 3) In the formula, A represents —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ , —C≡C—, —R ⁹ C═. CR ^10- , wherein R ^{9 to} R ¹⁰ are each independently a group including a structure represented by hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms.

  Moreover, in the photosensitive resin composition by this invention, the said (a) component is represented by the general formula (II) shown below, It is characterized by the above-mentioned.

（式中、Ｒ¹、Ｒ²は各々独立に水素、フッ素又は炭素数１〜６のアルキル基、Ｕは２価の有機基であり、ｎは１〜３０の整数である。）

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, U is a divalent organic group, and n is an integer of 1 to 30.)

  Moreover, in the photosensitive resin composition by this invention, n in general formula (II) of the said (a) component is represented by 7-30, It is characterized by the above-mentioned.

  Moreover, in the photosensitive resin composition for low temperature curing by this invention, (a) General formula (III):

（式中、Ｕ, Ｖ, Ｗ, Ｘは２価の有機基を示し、Ｕ又はＶの少なくとも一方が炭素数１〜３０の脂肪族鎖状構造を含む基であり、ｊ及びｋはＡ構造単位とＢ構造単位のモル分率を示し、ｊ及びｋの和は１００モル％である。）で示されるＡ構造単位とＢ構造単位からなるポリベンゾオキサゾール前駆体の共重合体と、（ｂ）感光剤と、及び（ｃ）溶剤とを含有してなることを特徴とする。

(In the formula, U, V, W and X represent a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms, and j and k are A structures. A copolymer of a polybenzoxazole precursor composed of an A structural unit and a B structural unit represented by (b is a molar fraction of units and B structural units, and the sum of j and k is 100 mol%); It comprises a photosensitizer and (c) a solvent.

  In the photosensitive resin composition according to the present invention, at least one of U and V in the general formula (III) of the component (a) is represented by the following general formula (UV1):

（式中、Ｒ¹、Ｒ²は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、aは１〜３０の整数を示す。）で表される構造を含む基、または一般式（ＵＶ２）：

(Wherein R ¹ and R ² are each independently hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30), or a general group Formula (UV2):

（式中、Ｒ³〜Ｒ⁸は、各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、aからｃは各々独立に１〜６の整数を表し、ｄは０〜３の整数である。また、式中Ａは−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂、−Ｃ≡Ｃ−、−Ｒ⁹Ｃ＝ＣＲ¹⁰−である。Ｒ⁹〜Ｒ¹⁰は、各々独立に水素、フッ素又は炭素数１〜６のアルキル基。）で表される構造を含む基、であることを特徴とする。

(Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, a to c each independently represents an integer of 1 to 6, and d is 0 to 3) In the formula, A represents —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ , —C≡C—, —R ⁹ C═. CR ^10- , wherein R ^{9 to} R ¹⁰ are each independently a group including a structure represented by hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms.

  In the photosensitive resin composition for low-temperature curing according to the present invention, the component (a) is represented by the general formula (IV).

（式中、Ｒ¹、Ｒ²は各々独立に水素、フッ素又は炭素数１〜６のアルキル基、Ｕ,Ｗ,Ｘは２価の有機基を示し、ｊ及びｋはＡ構造単位とＢ構造単位のモル分率を示し、ｊ及びｋの和は１００モル％であり、ｎは１〜３０の整数である。）

Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, U, W, and X are divalent organic groups, j and k are an A structural unit and a B structure. The unit represents the mole fraction, the sum of j and k is 100 mol%, and n is an integer of 1 to 30.)

  Moreover, in the photosensitive resin composition by this invention, n in general formula (IV) of the said (a) component is represented by 7-30, It is characterized by the above-mentioned.

  Moreover, in the photosensitive resin composition by this invention, the said (b) component is a photosensitive agent which generate | occur | produces an acid or a radical by light.

  The photosensitive resin composition according to the present invention further includes a thermal acid generator that generates an acid by heating as the component (d).

  In addition, the polybenzoxazole film according to the present invention is formed by using the photosensitive resin composition and dehydrating and closing the polybenzoxazole precursor.

  Moreover, in the manufacturing method of the pattern cured film by this invention, the photosensitive resin film formation process of apply | coating the said photosensitive resin composition on a support substrate, and drying and forming the photosensitive resin film, and the said photosensitive property An exposure step of exposing the resin film to a predetermined pattern, a development step of developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a pattern resin film, and pattern curing by heating the pattern resin film And a heat treatment step for obtaining a film.

  In the method for producing a cured pattern film according to the present invention, the heat treatment step irradiates the pattern resin film with microwaves while changing the frequency of the microwaves. And

  In the method for producing a cured pattern film according to the present invention, the heat treatment temperature is 280 ° C. or lower in the step of heat-treating the photosensitive resin film after development.

  The electronic component according to the present invention is characterized in that a layer of a patterned cured film obtained by the method for producing a patterned cured film has an interlayer insulating film layer and / or a surface protective film layer.

  In the electronic component according to the present invention, the electronic component is a magnetoresistive memory.

  Conventionally, a polybenzoxazole precursor used as a base resin of a photosensitive resin composition needs to be cured at a high temperature of about 350 ° C. in order to perform dehydration and ring closure after pattern formation. On the other hand, the photosensitive resin composition of the present invention has a specific polybenzoxazole photosensitive resin film having a high dehydration ring closure rate as a base resin even at 280 ° C. or lower, and thereby the film after curing is cured. Performance comparable to those cured at high temperatures. Therefore, the cyclization reaction and the curing reaction occur efficiently at a lower temperature. Further, the photosensitive resin composition of the present invention shows a difference in dissolution rate (dissolution contrast) with respect to the developer between the exposed portion and the unexposed portion, and can form a desired pattern.

  In addition, according to the method for producing a cured pattern film of the present invention, the use of the photosensitive resin composition is excellent in sensitivity, resolution, and adhesiveness, and is excellent in heat resistance even in a low-temperature curing process, and has a low water absorption rate. A pattern with a simple shape can be obtained.

  Furthermore, since the electronic component of the present invention is formed using the photosensitive resin composition of the present invention as a cured film that is a constituent element of the electronic component, it has a pattern cured film excellent in shape, adhesion, and heat resistance. . The electronic component of the present invention is highly reliable because the cured film can be cured by a low-temperature process, so that damage to the device can be avoided. In addition, the electronic component of the present invention has an advantage that the manufacturing yield is high because there is little damage to the device in the process.

  EMBODIMENT OF THE INVENTION Below, photosensitive resin composition by this invention, the manufacturing method of the pattern cured film using this resin composition, and one Embodiment of electronic component are described in detail based on drawing. In addition, this invention is not limited by the following embodiment.

[Photosensitive resin composition]
First, the photosensitive resin composition for low temperature hardening by this invention is demonstrated. The photosensitive resin composition according to the present invention comprises (a) general formula (I):

（式中、Ｕ又はＶは２価の有機基を示し、Ｕ又はＶの少なくとも一方が炭素数１〜３０の脂肪族鎖状構造を含む基である。）で示される繰り返し単位を有するポリベンゾオキサゾール前駆体と、（ｂ）感光剤と、及び（ｃ）溶剤とを含有する。なお、（ａ）ポリベンゾオキサゾール前駆体の共重合体、（ｂ）感光剤及び（ｃ）溶剤を、本明細書の記載において、場合によりそれぞれ単に（ａ）成分、（ｂ）成分及び（ｃ）成分と記す。

(In the formula, U or V represents a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms.) It contains an oxazole precursor, (b) a photosensitizer, and (c) a solvent. In the description of the present specification, (a) a polybenzoxazole precursor copolymer, (b) a photosensitizer and (c) a solvent are sometimes simply referred to as (a) component, (b) component and (c), respectively. ) Ingredients.

  Further, instead of the polybenzoxazole precursor having the repeating unit represented by the general formula (I), a polybenzoxazole precursor having the repeating unit represented by the following general formula (III) is used as the component (a). You can also

（式中、Ｕ, Ｖ, Ｗ, Ｘは２価の有機基を示し、Ｕ又はＶの少なくとも一方が炭素数１〜３０の脂肪族鎖状構造を含む基であり、ｊ及びｋはＡ構造単位とＢ構造単位のモル分率を示し、ｊ及びｋの和は１００モル％である。）

(In the formula, U, V, W and X represent a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms, and j and k are A structures. The mole fraction of the unit and the B structural unit is shown, and the sum of j and k is 100 mol%.)

Hereinafter, each component of the photosensitive resin composition by this invention is demonstrated.
(Component (a): polybenzoxazole precursor and copolymer of polybenzoxazole precursor)
Since the polybenzoxazole precursor and the polybenzoxazole precursor copolymer are usually developed with an alkaline aqueous solution, it is preferable that the polybenzoxazole precursor is soluble in an alkaline aqueous solution. In the present invention, for example, the structure of polyamide that is not a polybenzoxazole precursor other than the general formulas (I) and (III), the structure of polybenzoxazole, a polyimide or a polyimide precursor (polyamic acid or polyamic acid ester) You may have a structure with the structure of the copolymer of the polyoxazole precursor of the said general formula (I) and (III), and a polybenzoxazole precursor.

  In addition, alkaline aqueous solution is alkaline solutions, such as tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution. The structure of the copolymer of the polyoxazole precursor and the polybenzoxazole precursor, that is, the amide unit containing a hydroxy group represented by the general formulas (I) and (III) is finally dehydrated and closed during curing. Is converted into an oxazole body having excellent heat resistance, mechanical properties, and electrical properties.

The polybenzoxazole precursor used in the present invention has a repeating unit represented by the general formulas (I) and (III), but its solubility in an alkaline aqueous solution is an OH group bonded to U (generally a phenolic hydroxyl group). ), The amide unit containing the OH group is preferably contained in a certain proportion or more.
For example, a polyimide precursor represented by the following general formulas (V) and (VI) is preferable.

（式中、Ｕ，Ｖ，Ｙ，Ｚは２価の有機基を示す。ｊとｌは、それぞれの繰り返し単位のモル分率を示し、ｊとｌの和は１００モル％であり、ｊが６０〜１００モル％、ｌが４０〜０モル％である。）
ここで、式中のｊとｌのモル分率は、ｊ＝８０〜１００モル％、ｌ＝２０〜０モル％であることがより好ましい。

(In the formula, U, V, Y, and Z represent a divalent organic group. J and l represent the mole fraction of each repeating unit, and the sum of j and l is 100 mol%. 60-100 mol%, l is 40-0 mol%.)
Here, the molar fraction of j and l in the formula is more preferably j = 80 to 100 mol% and l = 20 to 0 mol%.

（式中、Ｕ, Ｖ, Ｗ, Ｘ, Ｙ, Ｚは２価の有機基を示す。ｊとｋとｌは、それぞれの繰り返し単位のモル分率を示し、ｊとｋとｌの和は１００モル％であり、ｊとｋの和ｊ＋ｋが６０〜１００モル％、ｌが４０〜０モル％である。）
ここで、式中のｊとｋとｌのモル分率は、ｊ＋ｋ＝８０〜１００モル％、ｌ＝２０〜０モル％であることがより好ましい。

(In the formula, U, V, W, X, Y, and Z represent divalent organic groups. J, k, and l represent the mole fraction of each repeating unit, and the sum of j, k, and l is 100 mol%, the sum of j and k, j + k is 60 to 100 mol%, and l is 40 to 0 mol%.)
Here, the molar fraction of j, k, and l in the formula is more preferably j + k = 80 to 100 mol% and l = 20 to 0 mol%.

  The molecular weight of the component (a) is preferably 3,000 to 200,000, more preferably 5,000 to 100,000 in terms of weight average molecular weight. Here, the molecular weight is a value obtained by measuring by a gel permeation chromatography method and converting from a standard polystyrene calibration curve.

  In the present invention, there is no particular limitation on the method for producing the polybenzoxazole precursor and the polybenzoxazole precursor copolymer. For example, polybenzoxazole having a repeating unit represented by the general formulas (I) and (III). The precursor can generally be synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting with the diamines. As the dihalide derivative, a dichloride derivative is preferable.

  The dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are used in the usual acid chlorideation reaction of carboxylic acid can be used.

  As a method of synthesizing the dichloride derivative, it can be synthesized by reacting the dicarboxylic acid derivative and the halogenating agent in a solvent, or reacting in an excess halogenating agent and then distilling off the excess. As the reaction solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, benzene and the like can be used.

  The amount of these halogenating agents to be used in a solvent is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol relative to the dicarboxylic acid derivative. When making it react in an agent, 4.0-50 mol is preferable and 5.0-20 mol is more preferable. The reaction temperature is preferably -10 to 70 ° C, more preferably 0 to 20 ° C.

  The reaction between the dichloride derivative and the diamine is preferably performed in an organic solvent in the presence of a dehydrohalogenating agent. As the dehydrohalogenating agent, organic bases such as pyridine and triethylamine are usually used. As the organic solvent, N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N, N-dimethylacetamide, N, N-dimethylformamide and the like can be used. The reaction temperature is preferably −10 to 30 ° C., more preferably 0 to 20 ° C.

  Hereinafter, the general formulas (I) and (III) will be described again, and then the polybenzoxazole precursor having the repeating units represented by the general formulas (I) and (III) will be described in detail.

（式中、Ｕ又はＶは２価の有機基を示し、Ｕ又はＶの少なくとも一方が炭素数１〜３０の脂肪族鎖状構造を含む基である。）

(In the formula, U or V represents a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms.)

（式中、Ｕ, Ｖ, Ｗ, Ｘは２価の有機基を示し、Ｕ又はＶの少なくとも一方が炭素数１〜３０の脂肪族鎖状構造を含む基であり、ｊ及びｋはＡ構造単位とＢ構造単位のモル分率を示し、ｊ及びｋの和は１００モル％である。）
ここで、式中のｊとｋのモル分率は、ｊ＝5〜８５モル％、ｋ＝１５〜９５モル％であることがパターン性、機械特性、耐熱性、耐薬品性の点でより好ましい。

(In the formula, U, V, W and X represent a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms, and j and k are A structures. The mole fraction of the unit and the B structural unit is shown, and the sum of j and k is 100 mol%.)
Here, the molar fraction of j and k in the formula is such that j = 5 to 85 mol% and k = 15 to 95 mol% in terms of pattern properties, mechanical properties, heat resistance, and chemical resistance. preferable.

A preferable group used as U in the general formulas (I) and (III) will be described.
The group containing an aliphatic chain structure having 1 to 30 carbon atoms may be present as U or V in the general formulas (I) and (III). As a group containing an aliphatic chain structure, a group containing a structure represented by the following general formula (UV1) or (UV2) is desirable in terms of high dehydration ring closure at 280 ° C. or lower. Furthermore, it is more preferable that the aliphatic linear structure has 7 to 30 carbon atoms because the elastic modulus is low and the elongation at break is high.

（式中、Ｒ¹、Ｒ²は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、aは１〜３０の整数を示す。）

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30.)

（式中、Ｒ³〜Ｒ⁸は、各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、aからｃは各々独立に１〜６の整数を表し、ｄは０〜３の整数である。また、式中Ａは−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂、−Ｃ≡Ｃ−、−Ｒ⁹Ｃ＝ＣＲ¹⁰−である。Ｒ⁹〜Ｒ¹⁰は、各々独立に水素、フッ素又は炭素数１〜６のアルキル基。）

(Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, a to c each independently represents an integer of 1 to 6, and d is 0 to 3) In the formula, A represents —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ , —C≡C—, —R ⁹ C═. CR ^10- , R ^{9 to} R ¹⁰ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms.)

  Examples of such diamines include

（式中ｎは1〜６の整数である。）が挙げられる。

(Wherein n is an integer of 1 to 6).

  Furthermore, as diamines used for U or W in the above general formulas (I) and (III), 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3 '-Dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1 , 1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Aromatic diamines can be mentioned, but are not limited thereto. These diamines can be used alone or in combination of two or more.

  In addition, when using the diamine which has these aliphatic chain structures, it is also possible to use together the diamine shown to the said Chemical formula (V) and General formula (VI) to such an extent that the effect of this invention is not impaired. is there.

Next, groups preferable as V in the general formulas (I) and (III) will be described.
The divalent organic group represented by V in the general formulas (I) and (III) is generally a dicarboxylic acid residue that reacts with a diamine to form a polyamide structure.
In the present invention, as V, a group containing an aliphatic chain structure having 1 to 30 carbon atoms may be present as U or V in the general formulas (I) and (III). As a group containing an aliphatic chain structure, when it has a structure represented by the following general formula (UV1) or (UV2), it has high heat resistance, high transparency in the ultraviolet and visible light range, and below 280 ° C. Is excellent in that it has a high dehydration ring closure rate. Furthermore, when the aliphatic linear structure has 7 to 30 carbon atoms, the polymer is easily soluble in solvents such as γ-butyrolactone and propylene glycol monomethyl ether acetate in addition to N-methyl-2-pyrrolidone, and storage stability is also improved. high. Furthermore, the elastic modulus is low and the elongation at break is high, which is more preferable.

（式中、Ｒ¹、Ｒ²は各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、aは１〜３０の整数を示す。）

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30.)

（式中、Ｒ³〜Ｒ⁸は、各々独立に水素、フッ素又は炭素数１〜６のアルキル基であり、aからｃは各々独立に１〜６の整数を表し、ｄは０〜３の整数である。また、式中Ａは−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＣＯ−、−ＮＨＣＯ−、−Ｃ（ＣＦ₃）₂、−Ｃ≡Ｃ−、−Ｒ⁹Ｃ＝ＣＲ¹⁰−である。Ｒ⁹〜Ｒ¹⁰は、各々独立に水素、フッ素又は炭素数１〜６のアルキル基。）

(Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, a to c each independently represents an integer of 1 to 6, and d is 0 to 3) In the formula, A represents —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ , —C≡C—, —R ⁹ C═. CR ^10- , R ^{9 to} R ¹⁰ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms.)

  Examples of the dicarboxylic acids as described above include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, and 2,2-dimethyl. Succinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3 -Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid , Suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluoroseba Acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosandioic acid, heneicosandioic acid , Docosane diacid, tricosane diacid, tetracosane diacid, pentacosane diacid, hexacosane diacid, heptacosane diacid, octacosane diacid, nonacosane diacid, triacontane diacid, hentriacontan diacid, dotriacontane diacid, Diglycolic acid and the following general formula:

（式中、Ｚは炭素数1〜６の炭化水素基、式中ｎは1〜６の整数である。）で示されるジカルボン酸等が挙げられる。

(Wherein, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6), and the like.

  As other dicarboxylic acids used as V, X or Z in the general formulas (I) and (III), isophthalic acid, terephthalic acid, 2,2-bis (4-carboxyphenyl) -1,1,1,3 , 3,3-hexafluoropropane, 4,4′-dicarboxybiphenyl, 4,4′-dicarboxydiphenyl ether, 4,4′-dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2,2 -Aromatic dicarboxylic acids such as bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalenedicarboxylic acid Etc. can be used together. These compounds can be used alone or in combination of two or more.

  In the case of the polybenzoxazole precursors represented by the general formulas (V) and (VI), the divalent organic group represented by Y in the formula generally reacts with a dicarboxylic acid to form a polyamide structure. It is a residue derived from diamine (except dihydroxydiamine that forms U). Y is preferably a divalent aromatic group or an aliphatic group. The number of carbon atoms is preferably 4 to 40, and more preferably a divalent aromatic group having 4 to 40 carbon atoms.

  Examples of such diamines include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p. -Phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4 Commercially available product name "LP" as aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, and other silicone-containing diamines. -7100 "," X-22-161AS "," X-2 2-161A "," X-22-161B "," X-22-161C "," X-22-161E "(all manufactured by Shin-Etsu Chemical Co., Ltd.), etc., but are not limited thereto. is not. These compounds are used alone or in combination of two or more.

((B) component: photosensitive agent)
The photosensitive resin composition of this invention contains the (b) photosensitive agent with the said polybenzoxazole precursor. This photosensitive agent has a function with respect to the developing solution of the film | membrane formed from the composition in response to light. Although there is no restriction | limiting in particular in the photosensitive agent used as (b) component by this invention, It is preferable that it generate | occur | produces an acid or a radical by light.

  In the case of the positive type, (b) the photosensitizer is more preferably one that generates an acid by light (photoacid generator). In the positive type, the photoacid generator has a function of generating an acid by light irradiation and increasing the solubility of the light irradiation portion in an alkaline aqueous solution. Examples of such photoacid generators include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and the like, and o-quinonediazide compounds are preferable because of their high sensitivity.

  The o-quinonediazide compound can be obtained, for example, by subjecting o-quinonediazidesulfonyl chlorides to a hydroxy compound, an amino compound or the like in the presence of a dehydrochlorinating agent. Examples of the o-quinonediazide sulfonyl chlorides include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. Etc. can be used.

  Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and 2,3,4-trihydroxybenzophenone. 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3,4, 3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro -1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] i Den, tris (4-hydroxyphenyl) methane, and tris (4-hydroxyphenyl) ethane can be used.

  Examples of the amino compound include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl. Sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3 -Amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-Amino-4-hydroxyphenyl) hexafluoropro Emissions, such as bis (4-amino-3-hydroxyphenyl) hexafluoropropane can be used.

  The o-quinonediazide sulfonyl chloride and the hydroxy compound and / or amino compound are blended so that the total of hydroxy group and amino group is 0.5 to 1 equivalent with respect to 1 mol of o-quinonediazide sulfonyl chloride. Is preferred. A preferred ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 to 1 / 0.95. A preferable reaction temperature is 0 to 40 ° C., and a preferable reaction time is 1 to 10 hours.

  As a reaction solvent for the above reaction, a solvent such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone or the like is used. Examples of dehydrochlorinating agents include sodium carbonate, sodium hydroxide, sodium bicarbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine.

  In the structure represented by U, V, X, Y in the general formulas (I) and (V), when there is a group having a photocrosslinkable group such as an acryloyl group or a methacryloyl group, the component (b) ( By using a radical generating substance, that is, a photopolymerization initiator as the photosensitive agent, it can be used as a negative photosensitive resin composition. This negative photosensitive resin composition has a function of reducing the solubility of the light irradiated portion in an alkaline aqueous solution by a crosslinking reaction by light irradiation.

  In the photosensitive resin composition of the present invention, the blending amount of the component (b) (photosensitive agent) is the component (a) (base resin) in terms of the difference in dissolution rate between the exposed part and the unexposed part and the allowable sensitivity range. ) 5 to 100 parts by weight is preferable with respect to 100 parts by weight, and 8 to 40 parts by weight is more preferable.

((C) component: solvent)
As component (c) (solvent) used in the present invention, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone Etc.

  These solvents can be used alone or in combination of two or more. Further, the amount of the solvent to be used is not particularly limited, but generally it is preferably adjusted so that the ratio of the solvent in the composition is 20 to 90% by weight.

((D) component: thermal acid generator)
In the present invention, a thermal acid generator (thermal latent acid generator) can be used as the component (d). The use of a thermal acid generator is preferable because the polybenzoxazole precursor, which is a phenolic hydroxyl group-containing polyamide structure, efficiently functions as a catalyst for causing a dehydration reaction and cyclization. In addition, the dehydration cyclization reaction can be further lowered by using this thermal acid generator in combination with a specific resin having a high degree of dehydration ring closure at about 280 ° C. or less according to the present invention, so that it can be cured even at low temperature curing. The performance of the physical properties of the later film is comparable to that obtained by curing at a high temperature.

  The acid generated from the thermal acid generator (thermal latent acid generator) is preferably a strong acid. Specifically, for example, p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, Preference is given to perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid. These acids efficiently act as a catalyst when the polybenzoxazole precursor phenolic hydroxyl group-containing polyamide structure undergoes a dehydration reaction and cyclizes. In contrast, acid generators that generate hydrochloric acid, bromic acid, iodic acid, and nitric acid have weak acidity and are likely to volatilize when heated. It is considered that it is hardly involved in the dehydration reaction, and it is difficult to obtain a sufficient effect of the present invention.

  These acids are added to the photosensitive resin composition of the present invention as a thermal acid generator in the form of a salt as an onium salt or in the form of a covalent bond such as imide sulfonate.

Examples of the onium salt include diaryl iodonium salts such as diphenyl iodonium salts, di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts, trialkylsulfonium salts such as trimethylsulfonium salts, dimethyl A dialkyl monoarylsulfonium salt such as a phenylsulfonium salt, a diarylmonoalkyliodonium salt such as a diphenylmethylsulfonium salt, and the like are preferable.
These are preferable because the decomposition start temperature is in the range of 150 to 250 ° C., and the polybenzoxazole precursor is efficiently decomposed during the cyclization dehydration reaction at 280 ° C. or less. On the other hand, triphenylsulfonium salt is not desirable as the thermal acid generator of the present invention. Since triphenylsulfonium salt has high thermal stability and generally has a decomposition temperature exceeding 300 ° C., no decomposition occurs during the cyclization dehydration reaction of the polybenzoxazole precursor at 280 ° C. or less, and a catalyst for cyclization dehydration. It is because it is thought that it does not work enough.

  From the above points, examples of the onium salt as the thermal acid generator include aryl sulfonic acid, camphor sulfonic acid, perfluoroalkyl sulfonic acid or diaryl iodonium salt of alkyl sulfonic acid, di (alkylaryl) iodonium salt, and trialkyl. A sulfonium salt, a dialkyl monoaryl sulfonium salt or a diaryl monoalkyl iodonium salt is preferred from the viewpoint of storage stability and developability. More specifically, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid (1% weight reduction temperature 180 ° C., 5% weight reduction temperature 185 ° C.), di (t-butylphenyl) trifluoromethanesulfonic acid Iodonium salt (1% weight loss temperature 151 ° C, 5% weight loss temperature 173 ° C), trimethylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 255 ° C, 5% weight loss temperature 278 ° C), trifluoromethanesulfonic acid Dimethylphenylsulfonium salt (1% weight loss temperature 186 ° C., 5% weight loss temperature 214 ° C.), diphenylmethylsulfonium salt of trifluoromethanesulfonic acid (1% weight loss temperature 154 ° C., 5% weight loss temperature 179 ° C.), Nonafluorobutanesulfonic acid di (t-butylphenyl) iodoni Can be mentioned salts, diphenyliodonium salts of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, dimethylphenyl sulfonium salt of benzenesulfonic acid, as preferred diphenyl methyl sulfonium salts of toluenesulfonic acid and the like.

  The imide sulfonate is preferably naphthoyl imide sulfonate. On the other hand, phthalimide sulfonate is not desirable because it has poor thermal stability, so that an acid is generated before the curing reaction and deteriorates storage stability. Specific examples of naphthoylimide sulfonate include 1,8-naphthoylimide trifluoromethylsulfonate (1% weight loss temperature 189 ° C., 5% weight loss temperature 227 ° C.), 2,3-naphthoylimide Trifluoromethylsulfonate (1% weight loss temperature 185 ° C., 5% weight loss temperature 216 ° C.) and the like can be mentioned as preferable examples.

Further, as the component (d) (thermal acid generator), as shown in the following chemical formula (VII), a compound having a structure of R ¹ R ² C═N—O—SO ₂ —R (weight loss of 1%) A temperature of 204 ° C., a 5% weight loss temperature of 235 ° C.) can also be used. Here, as R, for example, an aryl group such as a p-methylphenyl group and a phenyl group, an alkyl group such as a methyl group, an ethyl group and an isopropyl group, a perfluoroalkyl group such as a trifluoromethyl group and a nonafluorobutyl group Etc. Examples of R ¹ include a cyano group, and examples of R ² include a methoxyphenyl group and a phenyl group.

Further, as the component (d) (thermal acid generator), as shown in the following chemical formula (VIII), a compound having an amide structure —HN—SO ₂ —R (1% weight reduction temperature 104 ° C., 5% weight) A decreasing temperature of 270 ° C. can also be used. Here, examples of R include alkyl groups such as a methyl group, an ethyl group, and a propyl group, aryl groups such as a methylphenyl group and a phenyl group, and perfluoroalkyl groups such as a trifluoromethyl group and nonafluorobutyl. . Examples of the group to which —HN—SO ₂ —R is bonded include 2,2, -bis (4-hydroxyphenyl) hexafluoropropane, 2,2, -bis (4-hydroxyphenyl) propane, and di ( 4-hydroxyphenyl) ether and the like.

  In addition, as the component (d) (thermal acid generator) used in the present invention, a salt formed from a strong acid other than an onium salt and a base can also be used. Examples of such strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, and methanesulfone. Alkyl sulfonic acids such as acids, ethane sulfonic acids, butane sulfonic acids are preferred. As the base, for example, pyridine, alkylpyridine such as 2,4,6-trimethylpyridine, N-alkylpyridine such as 2-chloro-N-methylpyridine, halogenated-N-alkylpyridine and the like are preferable. More specifically, p-toluenesulfonic acid pyridine salt (1% weight loss temperature 147 ° C., 5% weight reduction temperature 190 ° C.), p-toluenesulfonic acid L-aspartic acid dibenzyl ester salt (1% weight) Decrease temperature 202 ° C, 5% weight loss temperature 218 ° C), 2,4,6-trimethylpyridine salt of p-toluenesulfonic acid, 1,4-dimethylpyridine salt of p-toluenesulfonic acid, etc., storage stability, development It is mentioned as a preferable thing from the point of property. These are also decomposed during the cyclization dehydration reaction of the polybenzoxazole precursor at 280 ° C. or less, and can act as a catalyst.

  The blending amount of the component (d) (thermal acid generator) is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight with respect to 100 parts by weight of the component (a) (base resin). 0.5-10 weight part is further more preferable.

[Other ingredients]
In the photosensitive resin composition according to the present invention, in addition to the components (a) to (d), (1) a dissolution accelerator, (2) a dissolution inhibitor, (3) an adhesion promoter, and (4) a surface activity. You may mix | blend components, such as an agent or a leveling agent.

((1) dissolution promoter)
In the present invention, a solubility promoter that promotes the solubility of the base resin as the component (a) in an alkaline aqueous solution, such as a compound having a phenolic hydroxyl group, can be further contained. The compound having a phenolic hydroxyl group can be added to increase the dissolution rate of the exposed area when developing with an aqueous alkaline solution, increasing the sensitivity, and preventing the film from melting when the film is cured after pattern formation. it can.

  The compound having a phenolic hydroxyl group that can be used in the present invention is not particularly limited. Examples of the low molecular weight compound having a phenolic hydroxyl group include o-cresol, m-cresol, p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, C, E, F and G, 4,4 ′, 4 ″ -methylidynetrisphenol, 2,6-[(2-hydroxy-5 -Methylphenyl) methyl] -4-methylphenol, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 4,4'-[ 1- [4- [2- (4-Hydroxyphenyl) -2-propyl] phenyl] ethylidene] bisphenol, 4,4 ′, 4 ″ -ethylidinetris 4- [bis (4-hydroxyphenyl) methyl] -2-ethoxyphenol, 4,4 ′-[(2-hydroxyphenyl) methylene] bis [2,3-dimethylphenol], 4,4′- [(3-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 4,4 ′-[(4-hydroxyphenyl) methylene] bis [2,6-dimethylphenol], 2,2 ′-[( 2-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 2,2 ′-[(4-hydroxyphenyl) methylene] bis [3,5-dimethylphenol], 4,4 ′-[(3 4-dihydroxyphenyl) methylene] bis [2,3,6-trimethylphenol], 4- [bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) methyl ] -1,2-benzenediol, 4,6-bis [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,2,3-benzenetriol, 4,4 ′-[(2-hydroxyphenyl) ) Methylene] bis [3-methylphenol], 4,4 ′, 4 ″-(3-methyl-1-propanyl-3-ylidine) trisphenol, 4,4 ′, 4 ″, 4 ′ ″- (1,4-phenylenedimethylidine) tetrakisphenol, 2,4,6-tris [(3,5-dimethyl-4-hydroxyphenyl) methyl] -1,3-benzenediol, 2,4,6-tris [ (3,5-dimethyl-2-hydroxyphenyl) methyl] -1,3-benzenediol, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -3,5-bis [( Hydroxy-3-methyl And phenyl) methyl] phenyl] -phenyl] ethylidene] bis [2,6-bis (hydroxy-3-methylphenyl) methyl] phenol.

  The low molecular weight compound having a phenolic hydroxyl group has a smaller effect on promoting the dissolution of the exposed portion when the molecular weight is increased. Among them, a compound having a molecular weight of 1,500 or less is preferable, and as such, the following general formula (VIV) Are particularly preferable because of the excellent balance between the effect of promoting dissolution of the exposed area and the effect of preventing melting during curing of the film.

（式中、Ｘは単結合又は２価の有機基を示し、各Ｒは各々独立にアルキル基又はアルケニル基を示し、ｍ及びｎは各々独立に１又は２であり、ｐ及びｑは各々独立に０〜３の整数である。）

(Wherein X represents a single bond or a divalent organic group, each R independently represents an alkyl group or an alkenyl group, m and n are each independently 1 or 2, and p and q are each independently It is an integer of 0 to 3).

  The blending amount of the component of the compound having a phenolic hydroxyl group is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the component (a) from the viewpoint of development time and the allowable width of the unexposed part remaining film ratio. More preferred is ˜25 parts by weight.

((2) dissolution inhibitor)
In the present invention, a dissolution inhibitor that is a compound that inhibits the solubility of the base resin as the component (a) in an alkaline aqueous solution can be further contained. Specific examples include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide.

  These may not easily participate in the cyclization dehydration reaction of the polybenzoxazole precursor because the generated acid is likely to volatilize. However, it effectively inhibits dissolution and helps to control the remaining film thickness and development time. The blending amount of the above component (dissolution inhibitor) is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the base resin as the component (a) from the viewpoint of sensitivity and an allowable range of development time. -30 parts by weight is more preferable, and 0.1-20 parts by weight is more preferable.

((3) Adhesion imparting agent)
The photosensitive resin composition of the present invention can contain an adhesion-imparting agent such as an organic silane compound or an aluminum chelate compound in order to enhance the adhesion of the cured film to the substrate.

  Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, ureapropyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n -Propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , N-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenyl Silanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4- Bis (ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyl Hydroxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxy) And silyl) benzene. Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like.

  When using these adhesiveness imparting agents, 0.1 to 30 parts by weight is preferable and 0.5 to 20 parts by weight is more preferable with respect to 100 parts by weight of component (a) (base resin).

((4) Surfactant or leveling agent)
In addition, the photosensitive resin composition of the present invention may be added with an appropriate surfactant or leveling agent in order to prevent coatability, for example, striation (film thickness unevenness) or improve developability. Can do.

  Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. “Megafax F171”, “F173”, “R-08” (above, manufactured by Dainippon Ink & Chemicals, Inc.), trade names “Florard FC430”, “FC431” (above, manufactured by Sumitomo 3M Limited), trade names “ And organosiloxane polymers KP341, KBM303, KBM403, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

[Method for producing patterned cured film]
Next, the manufacturing method of the pattern cured film by this invention is demonstrated. The method for producing a cured pattern film according to the present invention includes a photosensitive resin film forming step in which the above-described photosensitive resin composition is applied onto a support substrate and dried to form a photosensitive resin film. Through an exposure process for exposing the pattern, a development process for developing the exposed photosensitive resin film to obtain a pattern resin film, and a heat treatment process for obtaining a pattern cured film by heat-treating the pattern resin film, A pattern cured film of oxazole can be obtained. Hereinafter, each step will be described.

(Photosensitive resin film forming process)
First, in this step, the photosensitive resin composition of the present invention is used on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride using a spinner or the like. After spin coating, dry using a hot plate, oven, etc. Thereby, the photosensitive resin film which is a film of the photosensitive resin composition is obtained.

(Exposure process)
Next, in the exposure step, exposure is performed by irradiating the photosensitive resin film formed on the support substrate with an actinic ray such as an ultraviolet ray, visible ray, or radiation via a mask.

(Development process)
In the development step, a pattern cured film is obtained by removing the exposed portion of the photosensitive resin film exposed to actinic rays with a developer. Preferred examples of the developer include aqueous alkali solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. The base concentration of these aqueous solutions is preferably 0.1 to 10% by weight. Furthermore, alcohols and surfactants can be added to the developer and used. Each of these can be blended in the range of preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the developer.

(Heat treatment process)
Next, in the heat treatment step, the patterned resin film obtained after development can be heat-treated to form a heat-resistant polyoxazole pattern cured film having an oxazole ring or other functional group. The heating temperature in the heat treatment step is 280 ° C. or lower, desirably 120 to 280 ° C., more desirably 160 to 250 ° C.

  The heat treatment is performed using a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, or the like. In addition, either air or an inert atmosphere such as nitrogen can be selected. However, it is preferable to perform the treatment under nitrogen because the oxidation of the photosensitive resin composition film can be prevented. Since the said heating temperature range is lower than the conventional heating temperature, the damage to a support substrate or a device can be restrained small. Therefore, by using the pattern manufacturing method of the present invention, devices can be manufactured with high yield. It also leads to energy savings in the process.

  Further, as the heat treatment of the present invention, a microwave curing device or a variable frequency microwave curing device can be used in addition to using an ordinary nitrogen-substituted oven. By using these, it is possible to effectively heat only the photosensitive resin composition film while keeping the temperature of the substrate or device at, for example, 220 ° C. or lower.

  For example, in Japanese Patent Nos. 2587148 and 3031434, dehydration and ring closure of a polyimide precursor using microwaves are studied. In US Pat. No. 5,739,915, when a polyimide precursor thin film is dehydrated and closed using microwaves, there is a method for avoiding damage to the polyimide thin film or the base material by irradiating with the frequency changed in a short period. Proposed.

  When microwaves are irradiated in pulses while changing the frequency, standing waves can be prevented and the substrate surface can be heated uniformly. In addition, when the substrate includes metal wiring like an electronic component, it is possible to prevent the occurrence of discharge from the metal and to protect the electronic component from destruction by irradiating the microwave in pulses while changing the frequency. It is preferable in that it can be performed.

  The frequency of the microwaves irradiated when the polybenzoxazole precursor in the photosensitive resin composition of the present invention is dehydrated and cyclized is in the range of 0.5 to 20 GHz, but is practically preferably in the range of 1 to 10 GHz. Furthermore, the range of 2-9 GHz is more preferable.

  Although it is desirable to continuously change the frequency of the microwave to be irradiated, the irradiation is actually performed by changing the frequency stepwise. At that time, the shorter the time for irradiating a single-frequency microwave, the less likely it is that standing waves or metal discharges occur, and the time is preferably 1 millisecond or less, particularly preferably 100 microseconds or less.

  The output of the microwave to be irradiated varies depending on the size of the apparatus and the amount of the object to be heated, but is generally in the range of 10 to 2000 W, practically preferably 100 to 1000 W, more preferably 100 to 700 W, further preferably 100 to 700 W. 500 W is most preferred. If the output is 10 W or less, it is difficult to heat the object to be heated in a short time, and if it is 2000 W or more, a rapid temperature rise tends to occur.

  As described above, the temperature at which the polybenzoxazole precursor in the photosensitive resin composition of the present invention is subjected to dehydration and ring closure by microwaves is also used to avoid damage to the polybenzoxazole thin film and the substrate after dehydration and ring closure. The lower one is preferable. In the present invention, the temperature for dehydration and ring closure is preferably 280 ° C. or lower, more preferably 250 ° C. or lower, more preferably 220 ° C. or lower, and most preferably 220 ° C. or lower. The substrate temperature is measured by a known method such as infrared or GaAs thermocouples.

  The microwave irradiated when dehydrating and ring-closing the polybenzoxazole precursor in the photosensitive resin composition of the present invention is preferably turned on / off in pulses. By irradiating the microwaves in a pulsed manner, the set heating temperature can be maintained, and damage to the polybenzoxazole thin film and the substrate can be avoided. Although the time for irradiating the pulsed microwave at one time varies depending on the conditions, it is approximately 10 seconds or less.

  The time for dehydrating and ring-closing the polybenzoxazole precursor in the photosensitive resin composition of the present invention is the time until the dehydrating and ring-closing reaction sufficiently proceeds, but is generally about 5 hours or less in view of work efficiency. The atmosphere of dehydration ring closure can be selected from the air or an inert atmosphere such as nitrogen.

  In this way, the substrate having the photosensitive resin composition of the present invention as a layer is irradiated with microwaves under the above-described conditions to dehydrate and cyclize the polybenzoxazole precursor in the photosensitive resin composition of the present invention. For example, a polyoxazole having no difference from the physical properties of a dehydration ring closure film at a high temperature using a thermal diffusion furnace can be obtained even by a dehydration ring closure process at a low temperature using microwaves.

[Semiconductor device manufacturing process]
Next, as an example of a pattern manufacturing method according to the present invention, a semiconductor device manufacturing process will be described with reference to the drawings. 1 to 5 are schematic cross-sectional views for explaining a manufacturing process of a semiconductor device having a multilayer wiring structure, and represent a series of processes from a first process to a fifth process.

  In these drawings, a semiconductor substrate 1 such as a Si substrate having a circuit element (not shown) is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and the first circuit element is exposed on the first circuit element. A conductor layer 3 is formed. A film made of polyimide resin or the like as the interlayer insulating film layer 4 is formed on the semiconductor substrate by a spin coating method or the like (first step, FIG. 1).

  Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film layer 4 as a mask by a spin coating method, and a predetermined portion of the interlayer insulating film layer is formed by a known photolithography technique. A window 6A is provided so that 4 is exposed (second step, FIG. 2). The interlayer insulating film layer 4 in the window 6A is selectively etched by dry etching means using a gas such as oxygen or carbon tetrafluoride to open the window 6B. Next, the photosensitive resin layer 5 is completely removed using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B (third step, FIG. 3).

  Further, the second conductor layer 7 is formed by using a known photolithography technique, and the electrical connection with the first conductor layer 3 is completely performed (fourth step, FIG. 4). When a multilayer wiring structure having three or more layers is formed, each layer can be formed by repeating the above steps.

  Next, the surface protective film 8 is formed. In the example of FIGS. 1-5, this surface protective film is formed as follows. That is, the photosensitive resin composition of the present invention is applied and dried by a spin coating method, irradiated with light from a mask on which a pattern for forming a window 6C is formed at a predetermined portion, and then developed with an alkaline aqueous solution. A pattern resin film is formed. Thereafter, the patterned resin film is heated to form a polybenzoxazole pattern cured film as the surface protective film layer 8 (fifth step, FIG. 5). The surface protective film layer (polybenzoxazole pattern cured film) 8 protects the conductor layer from external stress, α rays, and the like, and the obtained semiconductor device is excellent in reliability.

In the present invention, in the heating step for forming the polybenzoxazole film, which conventionally required a high temperature of about 350 ° C., curing can be performed by using a low temperature heating of 280 ° C. or less. Even in the case of curing at 280 ° C. or lower, the photosensitive resin composition of the present invention undergoes sufficient cyclization dehydration reaction, so that the film physical properties (elongation, water absorption, weight loss temperature, outgas, etc.) are cured at 300 ° C. or higher. The change in physical properties is small as compared with the case of the above. Therefore, since the process can be performed at a low temperature, defects due to heat of the device can be reduced, and a highly reliable semiconductor device (electronic component) can be obtained with high yield.
In the above example, the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.

[Electronic parts]
Next, the electronic component according to the present invention will be described. The electronic component according to the present invention has a pattern cured film formed by the above-described method for producing a pattern cured film using the photosensitive resin composition described above. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like. In particular, MRAM (Magnetic Resistive Random Access Memory) having low heat resistance is preferable.

  In addition, the pattern cured film can be used specifically for forming a surface protective film for an electronic component such as a semiconductor device, an interlayer insulating film, an interlayer insulating film for a multilayer wiring board, and the like. The electronic component according to the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the photosensitive resin composition, and can have various structures. For example, the photosensitive resin composition of the present invention is suitable for an MRAM surface protective film.

  Hereinafter, based on an Example and a comparative example, it demonstrates further more concretely about this invention. In addition, this invention is not limited to the following Example.

Synthesis Example 1 Synthesis of Polybenzoxazole Precursor In a 0.2 liter flask equipped with a stirrer and a thermometer, 60 g of N-methylpyrrolidone was charged and 2,2′-bis (3-amino-4-hydroxy 13.92 g of phenyl) hexafluoropropane was added and dissolved by stirring. Subsequently, while maintaining the temperature at 0 to 5 ° C., 5.64 g of malonic dichloride was added dropwise over 10 minutes, and then stirring was continued for 60 minutes. The obtained solution was poured into 3 liters of water, and the precipitate was collected. This was washed three times with pure water, and then reduced in pressure to obtain polyhydroxyamide (polybenzoxazole precursor) (hereinafter, referred to as “polyhydroxyamide”). Polymer I). The polymer I had a weight average molecular weight of 11,500 and a dispersity of 1.7 determined by GPC standard polystyrene conversion.

(Synthesis Example 2)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with succinic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight of 20,400 and a dispersity of 1.8 determined by standard polystyrene conversion.

(Synthesis Example 3)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with glutaric acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer III) had a weight average molecular weight of 12,800 and a dispersity of 1.7 determined by standard polystyrene conversion.

(Synthesis Example 4)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the malonic acid dichloride used in Synthesis Example 1 was replaced with adipic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer IV) had a weight average molecular weight of 29,300 and a dispersity of 1.9 determined by standard polystyrene conversion.

(Synthesis Example 5)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with suberic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer V) had a weight average molecular weight of 36,900 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 6)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with sebacic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer VI) had a weight average molecular weight of 33,100 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 7)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that malonic acid dichloride used in Synthesis Example 1 was replaced with dodecanedioic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer VII) had a weight average molecular weight of 31,600 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 8)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the malonic acid dichloride used in Synthesis Example 1 was replaced with dimethylmalonic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer VIII) had a weight average molecular weight of 22,200 and a dispersity of 1.8 determined by standard polystyrene conversion.

(Synthesis Example 9)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the malonic acid dichloride used in Synthesis Example 1 was replaced with hexafluoroglutaric acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer VIV) had a weight average molecular weight of 10,700 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Synthesis Example 10)
The malonic acid dichloride used in Synthesis Example 1 was changed to glutaric acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was changed to 2,2′-bis (3-amino-4-hydroxyphenyl). ) Synthesis was performed under the same conditions as in Synthesis Example 1 except that isopropylidene was used. The obtained polyhydroxyamide (hereinafter referred to as “polymer X”) had a weight average molecular weight of 16,400 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Synthesis Example 11)
Malonic acid dichloride used in Synthesis Example 1 was converted to suberic acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was converted to 2,2′-bis (3-amino-4-hydroxyphenyl). ) Synthesis was performed under the same conditions as in Synthesis Example 1 except that isopropylidene was used. The resulting polyhydroxyamide (hereinafter referred to as polymer XI) had a weight average molecular weight of 33,400 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 12)
Malonic acid dichloride used in Synthesis Example 1 was changed to sebacic acid dichloride, and 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was changed to 2,2'-bis (3-amino-4-hydroxyphenyl). ) Synthesis was performed under the same conditions as in Synthesis Example 1 except that isopropylidene was used. The obtained polyhydroxyamide (hereinafter referred to as polymer XII) had a weight average molecular weight of 28,800 and a dispersity of 1.9, as determined by standard polystyrene conversion.

(Synthesis Example 13)
Malonic acid dichloride used in Synthesis Example 1 was changed to dodecanedioic acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was changed to 2,2′-bis (3-amino-4-hydroxy). Synthesis was carried out under the same conditions as in Synthesis Example 1 except that it was replaced with (phenyl) isopropylidene. The obtained polyhydroxyamide (hereinafter referred to as polymer XIII) had a weight average molecular weight of 24,300 and a dispersity of 1.9, as determined by standard polystyrene conversion.

(Synthesis Example 14)
The malonic acid dichloride used in Synthesis Example 1 was changed to dimethylmalonic acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was changed to 2,2′-bis (3-amino-4-hydroxy). Synthesis was carried out under the same conditions as in Synthesis Example 1 except that it was replaced with (phenyl) isopropylidene. The obtained polyhydroxyamide (hereinafter referred to as polymer XIV) had a weight average molecular weight of 29,100 and a dispersity of 1.9, as determined by standard polystyrene conversion.

(Synthesis Example 15)
The synthesis was performed under the same conditions as in Synthesis Example 3 except that 50 mol% of glutaric acid dichloride used in Synthesis Example 3 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer XV) had a weight average molecular weight of 34,800 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 16)
The synthesis was performed under the same conditions as in Synthesis Example 8 except that 50 mol% of dimethylmalonic acid dichloride used in Synthesis Example 8 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer XVI) had a weight average molecular weight of 36,200 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 17)
The synthesis was performed under the same conditions as in Synthesis Example 6 except that 40 mol% of sebacic acid dichloride used in Synthesis Example 6 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer XVII) had a weight average molecular weight of 45,100 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 18)
The synthesis was performed under the same conditions as in Synthesis Example 7 except that 40 mol% of dodecanedioic acid dichloride used in Synthesis Example 7 was replaced with 4,4′-diphenyl ether dicarboxylic acid dichloride. The obtained polyhydroxyamide (hereinafter referred to as polymer XVIII) had a weight average molecular weight of 41,800 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 19)
50 mol% of the dimethyl acid dichloride used in Synthesis Example 8 was converted to 4,4′-diphenyl ether dicarboxylic acid dichloride, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 2,2′-bis. The synthesis was performed under the same conditions as in Synthesis Example 8 except that (3-amino-4-hydroxyphenyl) isopropylidene was used. The obtained polyhydroxyamide (hereinafter referred to as polymer XVIV) had a weight average molecular weight of 36,200 and a dispersity of 2.0 determined by standard polystyrene conversion.

(Synthesis Example 20)
In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4′-diphenyl ether dicarboxylic acid and 90 g of N-methylpyrrolidone were charged, and the flask was cooled to 5 ° C., and then 12.64 g of thionyl chloride. Was added dropwise and reacted for 30 minutes to obtain a solution of 4,4′-diphenyl ether dicarboxylic acid chloride. Next, 87.5 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 18.31 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. After stirring and dissolving, 8.53 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 4,4′-diphenyl ether dicarboxylic acid chloride was added dropwise over 30 minutes, followed by stirring for 30 minutes. Continued. The solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer XX). The weight average molecular weight calculated | required by standard polystyrene conversion was 17,900, and dispersion degree was 1.5.

(Synthesis Example 21)
1,3-bis (carboxypropyl) tetramethyldisiloxane used in Synthesis Example 20 was converted to 4,4′-diphenyl ether dicarboxylic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was used. Synthesis was performed under the same conditions as in Synthesis Example 20, except that 2,2′-bis (3-amino-4-hydroxyphenyl) sulfone was used. The obtained polyhydroxyamide (hereinafter referred to as polymer XXI) had a weight average molecular weight of 13,700 and a dispersity of 1.5 determined by standard polystyrene conversion.

(Synthesis Example 22)
The synthesis was performed under the same conditions as in Synthesis Example 20, except that 1,3-bis (carboxypropyl) tetramethyldisiloxane used in Synthesis Example 20 was replaced with isophthalic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer XXII) had a weight average molecular weight of 21,600 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Measurement conditions of weight average molecular weight by GPC method)
Measuring device; Detector L4000 UV manufactured by Hitachi, Ltd.
Pump: Hitachi Ltd. L6000
C-R4A Chromatopac manufactured by Shimadzu Corporation
Measurement conditions: Column Gelpack GL-S300MDT-5 x 2 eluent: THF / DMF = 1/1 (volume ratio)
LiBr (0.03 mol / l), H ₃ PO ₄ (0.06 mol / l)
Flow rate: 1.0 ml / min, detector: UV 270 nm
The measurement was performed using a solution of 1 ml of a solvent [THF / DMF = 1/1 (volume ratio)] with respect to 0.5 mg of the polymer.

(Examples 1-19 and Comparative Examples 1-3)
A resin solution obtained by dissolving 10.0 g of the polybenzoxazole precursor obtained in Synthesis Examples 1 to 22 in 15 g of N-methylpyrrolidone was spin-coated on a silicon wafer and dried at 120 ° C. for 3 minutes. A coating film (A) having a film thickness of 12 μm was obtained. This coating film was heated in an inert gas oven manufactured by Koyo Thermo Systems Co., Ltd. in a nitrogen atmosphere at 150 ° C. for 30 minutes, and further heated at 200 ° C. for 1 hour or 350 ° C. for 1 hour to obtain a cured film (cured at 200 ° C. A film (B) and a cured film (C) heated at 350 ° C. were obtained. The infrared absorption spectra of these coating films (A), cured films (B), and (C) were measured, and the absorbance at the peak due to CN stretching vibration near 1540 cm ⁻¹ was determined. For the measurement of the infrared absorption spectrum, “FTIR-8300” (trade name, manufactured by Shimadzu Corporation) was used as a measuring apparatus. The dehydration ring closure rate of the cured film (B) was calculated from the following formula, assuming that the dehydration ring closure rate of the coating film (A) was 0% and the dehydration ring closure rate of the cured film (C) was 100%.

(Measurement of transmittance)
A resin solution obtained by dissolving 10.0 g of the polybenzoxazole precursor and polyimide precursor obtained in Synthesis Examples 1 to 22 in 15 g of N-methylpyrrolidone was spin-coated on a silicon wafer, and 120 ° C. on a hot plate. And dried for 3 minutes to obtain a coating film having a thickness of 10 μm. The transmittance of this coating film was measured with a UV-visible spectrophotometer (trade name “U-3310” manufactured by Hitachi, Ltd.) at a wavelength of 365 nm (i-line) at a film thickness of 10 μm.

  Table 1 shows the dehydration ring closure rate at 200 ° C. and the i-line transmittance of 10 μm thickness of each polymer obtained by using the above formula.

  From the above results, in the polymers of Examples 1 to 19, the dehydration ring closure rate at 200 ° C. exceeded 50% and reached nearly 90%, and the dehydration ring closure rate of the aromatic polybenzoxazole of Comparative Examples 1 to 3 was 15 to It was very high compared to 26%. Furthermore, the polymers of Examples 2 to 18 had a very high i-line transmittance of 70 μm and a thickness of 70% or more.

(Examples 20 to 38 and Comparative Examples 4 to 6)
(Photosensitive characteristic evaluation)
With respect to 100 parts by weight of the polybenzoxazole precursor as the component (a), the components (b) and (c) and other additive components are blended in the predetermined amounts shown in Table 2, and the photosensitive resin composition A solution was obtained.

  In the table, BLO represents γ-butyrolactone, PGMEA represents propylene glycol monomethyl ether acetate, NMP represents N-methylpyrrolidone, and BLO / PGMEA represents a mixture of both. The amount in parentheses indicates the amount added relative to 100 parts by weight of the polymer in parts by weight.

  In Table 2, B1, D1, D2, D3, and D4 are compounds represented by the following chemical formulas (X) and (XI), respectively.

  The solution of the photosensitive resin composition was spin coated on a silicon wafer to form a coating film having a dry film thickness of 10 to 15 μm, and i-line (365 nm) exposure was performed using LD5010i manufactured by Hitachi, Ltd. After exposure, heat at 120 ° C. for 3 minutes, develop with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide until the exposed silicon wafer is exposed, then rinse with water and the minimum exposure required for pattern formation And asked for resolution. The results are shown in Table 3.

  From the above results, it was found that the photosensitive compositions of Examples 20 to 38 using Polymers I to XVIV can draw a positive pattern with high sensitivity and resolution of 5 μm or 3 μm as in Comparative Examples 4 to 6.

  Next, the solution of the photosensitive resin composition was spin-coated on a silicon wafer and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 15 μm. Thereafter, the coating film was heated in an inert gas oven manufactured by Koyo Thermo Systems Co., Ltd. in a nitrogen atmosphere at 150 ° C. for 30 minutes, and further heated at 320 ° C. for 1 hour, 200 ° C. for 1 hour, or 180 ° C. for 1 hour. A cured film was obtained. Next, this cured film was peeled off using a 4.9% hydrofluoric acid aqueous solution, washed with water, dried, and then film properties such as glass transition point (Tg), elongation at break, elastic modulus, dielectric constant, and 5% weight loss temperature. I investigated. Tg was determined from the inflection point of thermal expansion using a TMA / SS6000 manufactured by Seiko Instruments Inc. at a heating rate of 5 ° C./min. The elongation at break and elastic modulus were obtained from a tensile test using an autograph AGS-100NH manufactured by Shimadzu Corporation. The pyrolysis temperature was measured using a TG / DTA6300 manufactured by Seiko Instruments Inc. under a flow of nitrogen gas of 200 mL / min under the condition of a heating rate of 10 ° C./min. The temperature at which the weight loss reached 5% It was temperature. The dielectric constant is formed by forming an aluminum film on the cured film with a vacuum deposition apparatus (manufactured by ULVAC), and charging the sample with an LF impedance analyzer (manufactured by Yokogawa Electric Corporation: trade name “HP4192A”). -It measured on the conditions of the usage frequency of 10 kHz using the apparatus which connected the fixture (the Yokogawa Electric make: brand name "HP16451B"). The relative dielectric constant was calculated from the measured charge capacity by the following formula.

  Further, the dehydration ring closure rate of the cured film was measured by the same method as described above. The measurement results of these various physical properties are shown in Tables 4 and 5.

  As described above, the resin compositions of Examples 20 to 38, which are the photosensitive resin compositions of the present invention, have Tg and elongation at break at 180 ° C. and 200 ° C. as compared with the resin compositions of Comparative Examples 4 to 6. However, it was confirmed that the change was small compared to when cured at 320 ° C., and the film physical properties were inferior.

  Regarding the 5% weight loss temperature, the value when cured at 180 ° C. and 200 ° C. was lower than when cured at 320 ° C., but 180% compared with the resin compositions of Comparative Examples 4-6. It was as high as 230 ° C. or higher for curing at 200 ° C. and 300 ° C. or higher for curing at 200 ° C.

  Regarding the dehydration ring closure rate, the resin compositions of Examples 20 to 38 had a dehydration change rate of 50% or higher when cured at 180 ° C, and already 70% or higher when cured at 200 ° C. The resin compositions of Examples 25 to 26, 31 to 32, and 36 to 37 using polymers having an alkyl chain length of 7 or more in the polybenzoxazole skeleton were broken as compared with the resin compositions of Comparative Examples 4 to 6 The elongation was as high as 10% or more when cured at 180 ° C., 200 ° C., and 320 ° C.

  Further, the resin compositions of Examples 25-26 and 31-32 all had low elastic modulus of 2.0 GPa or less and a dielectric constant of 3.0 or less when cured at 180 ° C., 200 ° C., and 320 ° C. It was low and excellent.

  On the other hand, when the resin compositions of Comparative Examples 4 to 6 were cured at 200 ° C., the dehydration ring closure rate was 42% or less and the progress of the cyclization dehydration reaction was insufficient. The weight reduction temperature was as low as 266 ° C. or lower. Similarly, the resin compositions of Comparative Examples 4 to 6 were insufficiently cyclized with a dehydration ring closure rate of 15% or less when cured at 180 ° C., and a dielectric constant of 4.0 or more and a 5% weight loss temperature was as low as 200 ° C. or less. .

  As described above, the photosensitive resin composition of the present invention is excellent in heat resistance even when used in a low temperature curing process, and a patterned cured film having a good shape can be obtained. Therefore, electronic components, particularly low temperature curing is required. Suitable for manufacturing MRAM and the like.

  Next, as shown in Table 6, the component (d) (thermal acid generator) was further added to the solutions prepared in Examples 20 to 38 and Comparative Examples 4 to 6. In Table 6, the compounds represented by the following chemical formula (XII) were used for d1 to d4 of the component (d). A solution of these photosensitive resin compositions was spin coated on a silicon wafer and heated at 120 ° C. for 3 minutes to form a coating film having a thickness of 15 μm. Thereafter, the coating film was heated in an inert gas oven at 150 ° C. for 30 minutes in a nitrogen atmosphere, and further heated at 200 ° C. for 1 hour, 180 ° C. for 1 hour, or 160 ° C. for 1 hour to obtain a cured film. The dehydration cyclization rate when thermosetting at 200 ° C., 180 ° C. and 160 ° C. for 1 hour was measured. Furthermore, changes in the cured film were observed for each cured film when acetone, BLO: γ-butyrolactone, and NMP: N-methylpyrrolidone were deposited for 15 minutes at room temperature. The results are shown in Table 6. The cured film with cracks was marked in the table with x, and the cracked ones with circles.

  As is apparent from Table 6, by using a thermal acid generator in combination, the resin compositions of Examples 20 to 38 greatly increased the dehydration ring closure rate even when cured at 180 ° C. compared to the case where no addition was made, and at a lower temperature. However, a high cyclization rate of 70% or more could be obtained. The resin compositions of Comparative Examples 4 to 6 were insufficient with 39% or less. In addition, the resin compositions of Examples 20 to 38 have a cyclization rate of 20 to 60% even after curing at 160 ° C., whereas the resin compositions of Comparative Examples 4 to 6 have a cyclization of 10% or less. Showed the rate.

  Next, regarding chemical resistance, the resin compositions of Comparative Examples 4 to 6 crack in any solvent, whereas the resin compositions of Examples 22 to 24 and 29 to 30 are acetone or 160 ° C. When cured with N, cracks occurred in NMP, but showed excellent chemical resistance against BLO. On the other hand, the resin compositions of Examples 25-26 and 31-32 showed excellent chemical resistance to all of acetone, BLO, and NMP when cured at 160 ° C, 180 ° C, and 200 ° C.

  As described above, the photosensitive resin composition according to the present invention is suitable for forming a surface protective film, an interlayer insulating film of an electronic component such as a semiconductor device, and an interlayer insulating film of a multilayer wiring board.

  As described above, the photosensitive resin composition according to the present invention uses a specific polybenzoxazole photosensitive resin film having a high dehydration ring closure rate even at a low temperature as a base resin, so that the physical properties of the cured film are cured at a high temperature. Performance comparable to that obtained. Moreover, according to the method for producing a cured pattern film of the present invention, the use of the photosensitive resin composition is excellent in sensitivity, resolution, and adhesiveness, and also excellent in heat resistance even in a low-temperature curing process, low in water absorption, and good. A patterned cured film having a simple shape can be obtained. The pattern cured film obtained from the photosensitive resin composition of the present invention has excellent shape, adhesion, heat resistance, and can be cured by a low temperature process, thereby avoiding damage to the device and having high reliability. Parts are obtained. Therefore, the photosensitive resin composition of the present invention is useful for electronic components such as electronic devices, and is particularly suitable for magnetoresistive memories.

It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention. It is a schematic sectional drawing explaining the manufacturing process of the semiconductor device which has a multilayer wiring structure by embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor substrate 2 Protective film 3 1st conductor layer 4 Interlayer insulating film layer 5 Photosensitive resin layer 6A, 6B, 6C Window 7 2nd conductor layer 8 Surface protective film layer

Claims (16)

(A) General formula (I):

(In the formula, U or V represents a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms.) An oxazole precursor;
(B) a photosensitive agent;
(C) a solvent;
The photosensitive resin composition characterized by including. In the general formula (I), at least one of U and V is the following general formula (UV1):

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30), or a group having the structure General formula (UV2):

(Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, a to c each independently represents an integer of 1 to 6, and d is 0 to 3) In the formula, A represents —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ , —C≡C—, —R ⁹ C═. CR ^10- , wherein R ^{9 to} R ¹⁰ are each independently hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms.)
The photosensitive resin composition according to claim 1, wherein The component (a) is represented by the following general formula (II):

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, U is a divalent organic group, and n is an integer of 1 to 30.)
It is represented by these, The photosensitive resin composition of Claim 1 characterized by the above-mentioned.   The photosensitive resin composition according to claim 3, wherein n in the general formula (II) is 7 to 30. (A) The following general formula (III):

(In the formula, U, V, W and X represent a divalent organic group, and at least one of U or V is a group containing an aliphatic chain structure having 1 to 30 carbon atoms, and j and k are A structures. A copolymer of a polybenzoxazole precursor having an A structural unit and a B structural unit represented by the following formula: When,
(B) a photosensitive agent;
(C) a solvent;
The photosensitive resin composition characterized by including. In the general formula (III), at least one of U and V is the following general formula (UV1):

(Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, and a represents an integer of 1 to 30), or a group having the structure General formula (UV2):

(Wherein R ^{3 to} R ⁸ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, a to c each independently represents an integer of 1 to 6, and d is 0 to 3) In the formula, A is —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ , —C≡C—, —R ⁹ C═CR ^10. R ^{9 to} R ¹⁰ are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms.)
The photosensitive resin composition according to claim 4, wherein The component (a) is represented by the following general formula (IV):

Wherein R ¹ and R ² are each independently hydrogen, fluorine or an alkyl group having 1 to 6 carbon atoms, U, W, and X are divalent organic groups, j and k are an A structural unit and a B structure. The unit represents the mole fraction, the sum of j and k is 100 mol%, and n is an integer of 1 to 30.)
It is represented by these. The photosensitive resin composition of Claim 5 characterized by the above-mentioned.   The photosensitive resin composition according to claim 7, wherein n in the general formula (IV) is 7 to 30.   The photosensitive resin composition according to claim 1, wherein the component (b) is a photosensitive agent that generates an acid or a radical by light.   Furthermore, the thermal resin generator which generate | occur | produces an acid by heating is included as (d) component, The photosensitive resin composition of any one of Claims 1-9 characterized by the above-mentioned.   A polybenzoxazole formed by using the photosensitive resin composition according to any one of claims 1 to 10 and dehydrating and ring-closing the polybenzoxazole precursor (a), which is a component thereof. film.   A photosensitive resin film forming step in which the photosensitive resin composition according to any one of claims 1 to 10 is applied onto a support substrate and dried to form a photosensitive resin film; and the photosensitive resin film is predetermined. An exposure process for exposing the pattern, a development process for developing the exposed photosensitive resin film using an alkaline aqueous solution to obtain a pattern resin film, and a heating process for heating the pattern resin film to obtain a pattern cured film A process for producing a patterned cured film comprising a treatment step.   13. The method for producing a patterned cured film according to claim 12, wherein the heat treatment step irradiates the pattern resin film with microwaves while changing the frequency thereof.   The method for producing a cured pattern film according to claim 12 or 13, wherein a heat treatment temperature in the heat treatment step is 280 ° C or lower.   An electronic component comprising the patterned cured film obtained by the method for producing a patterned cured film according to any one of claims 12 to 14 as an interlayer insulating film layer and / or a surface protective film layer.   The electronic component according to claim 15, wherein the electronic component is a magnetoresistive memory.

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