JP4742995B2 - Photosensitive resin composition, pattern manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to a heat-resistant photosensitive resin composition containing a polybenzoxazole precursor having photosensitivity, a pattern production method using the heat-resistant photosensitive resin composition, and an electronic component.

  Conventionally, polyimide resins having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like have been used for surface protection films and interlayer insulating films of semiconductor elements. However, in recent years, as semiconductor devices have been highly integrated and increased in size, there has been a demand for thinner and smaller sealing resin packages, and LOC (lead-on-chip) and surface mounting methods such as solder reflow have been adopted. Therefore, a polyimide resin excellent in mechanical properties, heat resistance and the like has been required more than ever.

  On the other hand, photosensitive polyimide having a photosensitive property imparted to the polyimide resin itself has been used. However, when this is used, the pattern creation process can be simplified and complicated manufacturing processes can be shortened. A heat-resistant photoresist using a conventional photosensitive polyimide or its precursor and its application are well known. For negative photosensitive polyimide, a method of introducing a methacryloyl group into a polyimide precursor via an ester bond or an ionic bond (for example, see Patent Documents 1 to 4), a soluble polyimide having a photopolymerizable olefin (for example, Patent Document) 5-10), and a self-sensitized polyimide having an benzophenone skeleton and an alkyl group at the ortho position of an aromatic ring to which a nitrogen atom is bonded (see, for example, Patent Documents 11 and 12).

  Since the above negative photosensitive polyimide requires an organic solvent such as N-methylpyrrolidone for development, recently, a positive photosensitive resin that can be developed with an alkaline aqueous solution has been proposed. For positive photosensitive resins, a method of introducing an o-nitrobenzyl group into a polyimide precursor via an ester bond (see Non-Patent Document 1, for example), a naphthoquinonediazide compound mixed with a soluble hydroxylimide or polyoxazole precursor (For example, see Patent Documents 13 and 14), a method for introducing naphthoquinone diazide through an ester bond into a soluble polyimide (for example, see Non-Patent Document 2), a method for mixing naphthoquinone diazide into a polyimide precursor (for example, Patent Document 15).

  However, the above-mentioned negative photosensitive polyimide has a problem in terms of function and resolution, and may cause a decrease in manufacturing yield depending on the application. Further, since the structure of the polymer to be used is limited, the physical properties of the finally obtained film are limited, which is unsuitable for multipurpose use. On the other hand, the positive type photosensitive resin also has the same problems because the sensitivity and resolution are low and the structure is limited due to the problem with the absorption wavelength of the photosensitive agent as described above.

  Also, carboxylic acids such as polybenzoxazole precursor mixed with a diazonaphthoquinone compound (see, for example, Patent Document 16), or polyamic acid having a phenol moiety introduced via an ester bond (for example, see Patent Document 17). Instead of these, phenolic hydroxyl groups have been introduced, but these have insufficient developability, resulting in film loss at unexposed areas and peeling of the resin from the substrate.

  For the purpose of improving developability and adhesion, a mixture of polyamic acids having a siloxane moiety in the polymer skeleton has been proposed (for example, see Patent Documents 18 and 19). Storage stability deteriorates due to use. In addition, for the purpose of improving storage stability and adhesion, amine end groups sealed with a polymerizable group (see, for example, Patent Documents 20 to 22) have also been proposed. Since a diazoquinone compound containing a large number of aromatic rings is used as a low-sensitivity, it is necessary to increase the addition amount of the diazoquinone compound, and there is a problem that the mechanical properties after thermosetting are remarkably lowered, and it is difficult to say that the material is at a practical level. Is.

  In order to improve the problems of the diazoquinone compound, those using various chemical amplification systems have been proposed. Chemically amplified polyimides (for example, see Patent Document 23), chemically amplified polyimides or polybenzoxazole precursors (for example, see Patent Documents 24 to 30), among which high-sensitivity ones have a low molecular weight However, those having excellent film characteristics exhibit a decrease in sensitivity due to insufficient solubility due to the high molecular weight, and it is difficult to say that these are materials of practical level. Therefore, in reality, none of them is sufficient for practical use.

Japanese Patent Laid-Open No. 49-11541 Japanese Patent Laid-Open No. 50-40922 JP 54-145794 A JP-A-56-38038, etc. JP 59-108031 A JP 59-220730 A JP 59-232122 A Japanese Unexamined Patent Publication No. 60-6729 JP-A-60-72925 JP 61-57620 A, etc. JP 59-219330 A JP 59-231533 A Japanese Examined Patent Publication No. 64-60630 US Pat. No. 4,395,482 JP 52-13315 A JP-A-1-46862 JP-A-10-307393 JP-A-4-31861 Japanese Patent Laid-Open No. 4-46345 JP-A-5-197153 JP-A-9-183846 JP 2001-183835 A Japanese Patent Laid-Open No. 3-763 JP 7-219228 A Japanese Patent Laid-Open No. 10-186664 Japanese Patent Laid-Open No. 11-202489 JP 2000-56559 A JP 2001-194791 A JP 2002-526793 A US Pat. No. 6,143,467 J. et al. Macromol. Sci. Chem. , A24, 10, 1407, 1987 Macromolecules, 23, 1990

  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 appeared 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 conventional problems as described above, and a polybenzoxazole photosensitive resin film having a specific structural unit having a high dehydration ring closure rate even at 280 ° C. or lower is used as a base resin. Thus, an object of the present invention is to provide a photosensitive resin composition, a pattern manufacturing method, and an electronic component in which the physical properties of a cured film are inferior to those cured at a high temperature.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, a buffer coating material that can be cured at a temperature of about 280 ° C. or less that is compatible with alkali development and has heat resistance, chemical resistance, and water-resistant adhesion. I found it. That is, as a result of detailed studies, the structural unit A of the general formula (I) shown below has a specific skeleton with a high dehydration ring closure rate, so that the physical properties of the cured film at high temperatures are different from those of the cured film even at low temperatures. The present invention provides a photosensitive resin composition rich in heat resistance such that there is no ink.

In addition, the present invention provides a pattern with a good shape that can be developed with an aqueous alkaline solution by using the photosensitive resin composition, has excellent sensitivity and resolution, and has excellent heat resistance by a low-temperature curing process at 280 ° C. or lower. The manufacturing method of the pattern obtained is provided.
Furthermore, the present invention provides a highly reliable electronic component with a high yield by avoiding damage to the device by having a pattern having a good shape and characteristics and being cured by a low temperature process.

〔式中、Ｕ, Ｖ, Ｗ, Ｘは２価の有機基を示し、ＵとＷが異なる基であるかＶとＸが異なる基であるか又はこれらのＵとＷ及びＶとＸの双方とも異なる基であり、ｊ及びｋはそれぞれＡ構造単位及び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、前記Ｕ及びＶの少なくとも一方が、以下に示す一般式（ＵＶ１）〜（ＵＶ５）のいずれかで表される構造を含む基である。〕 That is, the photosensitive resin composition according to the present invention includes (a) a copolymer of a polybenzoxazole precursor having an A structural unit and a B structural unit represented by the general formula (I), and (b) It contains a photosensitizer and (c) a solvent.

[In the formula, U, V, W, and X represent divalent organic groups, and U and W are different groups or V and X are different groups, or both U and W, and V and X are both J and k represent the mole fractions of the A structural unit and the B structural unit, respectively, the sum of j and k is 100 mole%, and at least one of the U and V is represented by the following general formula: It is a group including a structure represented by any one of formulas (UV1) to (UV5). ]

（但し、Ｘは２価の有機基である。）で表される構造を含む基、 (UV1): a group containing an alicyclic structure having 6 to 20 carbon atoms,
(UV2):

(Wherein X is a divalent organic group),

（但し、Ｒは各々独立に水素原子又は一価の有機基であり、Ｍは単結合又は２価の有機基であり、ｇ及びｈは各々独立に１〜４の整数を示し、ｏは０又は１である。）で表される構造を含む基、 (UV3):

(However, R is each independently a hydrogen atom or a monovalent organic group, M is a single bond or a divalent organic group, g and h each independently represent an integer of 1 to 4, and o is 0. Or a group comprising a structure represented by 1),

（但し、Ｒは各々独立に水素原子又は一価の有機基であり、ｎは１〜６の整数を示す。）で表される構造を含む基、及び (UV4):

Wherein R is independently a hydrogen atom or a monovalent organic group, and n is an integer of 1 to 6, and a group comprising a structure represented by:

（但し、Ｒは各々独立に水素原子又は一価の有機基であり、Ｒ'は各々独立に２価の有機基であり、ｍは１〜１００の整数を示す。） (UV5):

(However, R is a hydrogen atom or a monovalent organic group each independently, R 'is a bivalent organic group each independently, and m shows the integer of 1-100.)

  In the photosensitive resin composition according to the present invention, the component (a) is a copolymer of a polybenzoxazole precursor composed of an A structural unit and a B structural unit represented by the general formula (I). In the general formula (I), j and k represent the mole fractions of the A structural unit and the B structural unit, respectively, and the sum of j and k is 100 mol%, j is 1 to 99 mol%, k is 1 to 1 It is characterized by being in the range of 99 mol%.

  In the photosensitive resin composition according to the present invention, in the general formula (I) of the component (a), at least one of U and V is represented by the following general formulas (II), (III), (IV ) Or (V), which is a divalent organic group containing an alicyclic structure having 6 to 20 carbon atoms.

（一般式（ＩＩ）、（ＩＩＩ）、（ＩＶ）及び（Ｖ）中、Ｒ¹からＲ²¹は各々独立に水素又は炭素数１〜６のアルキル基であり、ｓ，ｔ，ｕ，ｖは各々独立に１〜６の整数を表す。）

(In the general formulas (II), (III), (IV) and (V), R ¹ to R ²¹ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and s, t, u and v are Each independently represents an integer of 1-6.)

  In the photosensitive resin composition according to the present invention, at least one of U and V in the general formula (I) of the component (a) has an adamantane structure as an alicyclic structure. .

  In the photosensitive resin composition according to the present invention, at least one of U and V in the general formula (I) of the component (a) is represented by the following general formula (VI) or (VII). It is characterized by being.

（一般式（ＶＩ）、（ＶＩＩ）中、Ｒ²²からＲ²⁷は各々独立に水素又は炭素数１〜６のアルキル基であり、ａ、ｂは各々独立に１〜６の整数を表す。）

(In the general formulas (VI) and (VII), R ²² to R ²⁷ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and a and b each independently represent an integer of 1 to 6)

（式中、Ｘは２価の有機基を示し、Ｒ²⁸及びＲ²⁹は各々独立に一価の有機基を示し、ｅ及びｆは各々独立に０〜４の整数である。） In the photosensitive resin composition according to the present invention, V is represented by the following general formula (VIII) in the general formula (I) of the component (a).

(In the formula, X represents a divalent organic group, R ²⁸ and R ²⁹ each independently represent a monovalent organic group, and e and f each independently represents an integer of 0 to 4.)

（一般式（ＩＸ）、（Ｘ）中、Ｍは単結合又は２価の有機基を示し、Ｒ³⁰〜Ｒ³⁵は各々独立に水素、炭素数１から６のアルキル基又は一価の有機基であり、ｇ、ｈはそれぞれ独立に１〜４の整数を表し、ｃ及びｄは各々独立に０〜４の整数を表す。） In the photosensitive resin composition according to the present invention, V is represented by the following general formula (IX) or (X) in the general formula (I) of the component (a). To do.

(In the general formulas (IX) and (X), M represents a single bond or a divalent organic group, and R ^{30 to} R ³⁵ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or a monovalent organic group. And g and h each independently represent an integer of 1 to 4, and c and d each independently represents an integer of 0 to 4.)

（式中、Ｒ³⁶、Ｒ³⁷は各々独立に水素又は炭素数１から６のアルキル基であり、ｎは１〜６の整数を表す。） In the photosensitive resin composition according to the present invention, U is represented by the following general formula (XI) in the general formula (I) of the component (a).

(In the formula, R ³⁶ and R ³⁷ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6)

（式中、Ｒ³⁸、Ｒ⁴³は各々独立に二価の有機基、Ｒ³⁹〜Ｒ⁴²は各々独立に水素又は炭素数１から６のアルキル基であり、ｍは１〜１００の整数を表す。） Moreover, in the photosensitive resin composition by this invention, V is represented by the following general formula (XII) in general formula (I) of the said (a) component.

Wherein R ³⁸ and R ⁴³ are each independently a divalent organic group, R ^{39 to} R ⁴² are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 100. .)

  Moreover, in the photosensitive resin composition by this invention, the sum of j and k is 100 mol% in said (a) general formula (I), j is 5-85 mol%, k is 15- It is characterized by being in the range of 95 mol%.

  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 method for producing a pattern according to the present invention, a step of applying the photosensitive resin composition on a supporting substrate and drying, and a step of exposing the photosensitive resin film obtained by the drying to a predetermined pattern And a step of developing the photosensitive resin film after the exposure using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after the development.

  Further, in the method for producing a pattern according to the present invention, in the step of heat-treating the photosensitive resin film after development, the heating step irradiates a pulsed microwave while changing the frequency. To do.

  In the pattern manufacturing method 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 pattern obtained by the pattern manufacturing method is provided as 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 random access memory (MRAM).

  Conventionally, the polybenzoxazole precursor used as the base resin of the photosensitive resin composition is cured at a high temperature of about 350 ° C. in order to perform dehydration and ring closure after pattern formation, but the photosensitive resin composition of the present invention is By using a polybenzoxazole photosensitive resin film having a plurality of structural units including a specific structural unit having a high dehydration ring closure rate even at 280 ° C. or lower as a base resin, the physical properties of the cured film are cured at a high temperature. Inferior performance is obtained. Therefore, the cyclization reaction and the curing reaction occur efficiently at a lower temperature. In addition, the photosensitive resin composition of the present invention has a large difference in dissolution rate (dissolution contrast) with respect to the developer between the exposed area and the unexposed area, and can form a desired pattern.

In addition, according to the method for producing a pattern of the present invention, the use of the composition makes it possible to obtain a pattern having a good shape with excellent sensitivity, resolution and adhesiveness, excellent heat resistance even in a low temperature curing process, and low water absorption. can get.
Furthermore, the electronic component of the present invention has a good shape, a pattern excellent in adhesiveness and heat resistance, and can be cured by a low-temperature process, thereby avoiding damage to the device and having high reliability. . In addition, since the damage to the device is small, the yield is high.

  EMBODIMENT OF THE INVENTION Below, photosensitive resin composition by this invention, the manufacturing method of a pattern, and one Embodiment of an 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 according to the present invention will be described. The photosensitive resin composition according to the present invention comprises (a) a copolymer of a polybenzoxazole precursor having an A structural unit and a B structural unit represented by the general formula (I), and (b) a photosensitive agent. And (c) a solvent. In some cases, the copolymer of (a) polybenzoxazole precursor, (b) photosensitizer and (c) solvent are simply referred to as component (a), component (b) and component (c), respectively.

［一般式（Ｉ）中、Ｕ, Ｖ, Ｗ, Ｘは２価の有機基を示し、Ｕ, Ｖの一方が以下に示す（ＵＶ１）〜（ＵＶ５）で表される構造を含む基のいずれかである。］

[In General Formula (I), U, V, W, and X represent divalent organic groups, and one of U and V includes any of the groups including structures represented by (UV1) to (UV5) shown below. It is. ]

（但し、Ｘは２価の有機基である。）で表される構造を含む基、 (UV1): a group containing an alicyclic structure having 6 to 20 carbon atoms,
(UV2)

(Wherein X is a divalent organic group),

（但し、Ｒは各々独立に水素原子又は一価の有機基であり、Ｍは単結合又は２価の有機基であり、ｇ及びｈは各々独立に１〜４の整数を示し、ｏは０又は１である。）で表される構造を含む基、 (UV3):

(However, R is each independently a hydrogen atom or a monovalent organic group, M is a single bond or a divalent organic group, g and h each independently represent an integer of 1 to 4, and o is 0. Or a group comprising a structure represented by 1),

（但し、Ｒは各々独立に水素原子又は一価の有機基であり、ｎは１〜６の整数を示す。）で表される構造を含む基、 (UV4):

(Wherein R is each independently a hydrogen atom or a monovalent organic group, and n is an integer of 1 to 6),

（但し、Ｒは各々独立に水素原子又は一価の有機基であり、Ｒ'は各々独立に２価の有機基であり、ｍは１〜１００の整数を示す）で表される構造を含む基。
以下、本発明による感光性樹脂組成物の各成分について説明する。 (UV5):

(Wherein R is each independently a hydrogen atom or a monovalent organic group, R ′ is each independently a divalent organic group, and m is an integer of 1 to 100). Group.
Hereinafter, each component of the photosensitive resin composition by this invention is demonstrated.

((A) component: copolymer of polybenzoxazole precursor)
Since the polybenzoxazole precursor is usually developed with an aqueous alkali solution, it is preferably soluble in the aqueous alkali solution. In the present invention, for example, the structure of a polybenzoxazole precursor other than the general formula (I), the structure of a polyamide that is not a polybenzoxazole precursor, the structure of a polybenzoxazole, a polyimide or a polyimide precursor (polyamide acid or polyamide) Acid ester) structure together with the structure of the polyoxazole precursor of the general formula (I).

  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 polyoxazole precursor, that is, the amide unit containing the hydroxy group represented by the general formula (I) is finally excellent in heat resistance, mechanical properties, and electrical properties due to dehydration and ring closure at the time of curing. Is converted to

  In the copolymer of polybenzoxazole precursor containing A structural unit and B structural unit represented by general formula (I) used in the present invention, U, V, W, and X are divalent in general formula (I). Wherein U and W are different groups, V and X are different groups, or both U and W and V and X are different groups. Moreover, j and k show the mole fraction of A structural unit and B structural unit, respectively, and the sum of j and k is 100 mol%, j is 1-99 mol%, k is 1-99 mol%. It is preferable. The molar fraction of j and k is more preferably j = 5 to 85 mol% and k = 15 to 95 mol% in terms of patternability, mechanical properties, heat resistance, and chemical resistance.

The dehydration ring closure rate of the polybenzoxazole precursor of component (a) is as follows: a film obtained by drying the coating film at 120 ° C. for 3 minutes, a film obtained by heating at 200 ° C. for 1 hour or 350 ° C. for 1 hour. The infrared absorption spectrum at the time of heat curing was measured and calculated from the absorbance of the peak due to the CN stretching vibration in the vicinity of 1540 cm ⁻¹ . In the low-temperature curing process at 280 ° C. or lower, the dehydration cyclization rate of the A structural unit polybenzoxazole precursor in the copolymer of the polybenzoxazole precursor composed of the A structural unit and the B structural unit represented by the general formula (I) is: It is preferably 30% or more from the viewpoint of heat resistance and low water absorption of the photosensitive resin composition.

  The polybenzoxazole precursor used in the present invention has two structural units represented by the above general formula (I), but its solubility in an aqueous alkali solution is an OH group bonded to a benzene ring bonded to U and W. Since it is derived from (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 formula (XIII) is preferable.

  In this general formula (XIII), U, V, W, X, Y, Z represent a divalent organic group. j, k and l represent the mole fraction of each repeating unit, the sum of j, k and l is 100 mol%, the sum of j and k is 60 to 100 mol%, and l is 40 to 0 mol. % Is preferred. Further, the molar fraction of j, k, and l is more preferably j + k = 80 to 100 mol%, and l = 20 to 0 mol%. In this case, as in the case of the general formula (I) for j and k, the sum of j and k is calculated as 100 mol%, j is 1 to 99 mol%, k is 1 to 99 mol%. It is preferable that j = 5 to 85 mol%, and k = 15 to 95 mol% is more preferable.

  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.

  There is no particular limitation on the method for producing the polybenzoxazole precursor in the present invention. For example, the polybenzoxazole precursor having a repeating unit represented by the general formula (I) is generally a dicarboxylic acid derivative and a hydroxy group-containing diamine. Can be synthesized. 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 used is preferably 1.5 to 3.0 mol, more preferably 1.7 to 2.5 mol, relative to 1 mol of the dicarboxylic acid derivative when reacted in a solvent. When making it react in a halogenating 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 formula (I) will be further described in detail.
First, a preferable group as U in general formula (I) will be described. In general formula (I), at least one of U and V is any of the groups including the structures represented by general formulas (UV1) to (UV5). (UV1): The group containing an alicyclic structure having 6 to 20 carbon atoms may be present as V ₁ or V _{2 in} place of U or V in U.

  In addition, in general formula (I), at least one of U and V is represented by the following general formula (II), (III), (IV) or (V). A divalent organic group containing is preferable.

（一般式（ＩＩ）、（ＩＩＩ）、（ＩＶ）、（Ｖ）中、Ｒ¹からＲ²¹は、各々独立に水素又は炭素数１〜６のアルキル基であり、ｓ，ｔ，ｕ，ｖは、各々独立に１〜６の整数を表す。）

(In the general formulas (II), (III), (IV), (V), R ¹ to R ²¹ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and s, t, u, v Each independently represents an integer of 1 to 6.)

As a group containing an alicyclic structure skeleton, a group containing an alicyclic structure or an adamantane structure represented by the above general formula (II), (III), (IV) or (V), heat resistance, ultraviolet In addition, it has transparency in the visible light amount range, and is preferable because it is excellent in terms of a high dehydration ring closure rate at 280 ° C. or lower.
The group containing an adamantane structure is preferably a group represented by the following general formula (VI) or (VII).

（一般式（ＶＩ）、（ＶＩＩ）中、Ｒ²²からＲ²⁷は、各々独立に水素又は炭素数１〜６のアルキル基であり、ａ、ｂは、各々独立に１〜６の整数を表す。）

(In the general formulas (VI) and (VII), R ²² to R ²⁷ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and a and b each independently represent an integer of 1 to 6) .)

  In addition, when a group described as (UV4) (preferably a group represented by the following general formula (XI), for example, an alkylene group or an alkylidene group) is included as a structure of U, in the heat resistance, ultraviolet, and visible light range. It is excellent in that it has a high degree of dehydration ring closure at 280 ° C. or less.

（式中、Ｒ³⁶、Ｒ³⁷は各々独立に水素又は炭素数１から６のアルキル基である。また、ｎは１〜６の整数を表す。）

(Wherein R ³⁶ and R ³⁷ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6)

  Examples of diamines used when synthesizing a polybenzoxazole precursor having a repeating unit represented by the general formula (I) include compounds represented by the following general formula (XIV).

（式中、Ｚは炭素数１〜６の炭化水素基、ｎは１〜６の整数である。）

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

  Next, as the diamine containing W which is a divalent organic group in the B structural unit of the general formula (I), 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 are preferred, but are not limited thereto. These diamines can be used alone or in combination of two or more.

On the other hand, the divalent organic group represented by V in the general formula (I) is generally a dicarboxylic acid residue that reacts with a diamine to form a polyamide structure.
In the present invention, examples of V include a group containing the above (UV1) alicyclic skeleton having 6 to 20 carbon atoms, and specifically, the general formula (II), (III), (IV) or (V And an adamantane structure represented by the above general formula (VI) or (VII).

The groups described as (UV2), (UV3) and (UV5) are also effective as V.
Specifically, a compound having a structure represented by the following general formula (VIII), (IX) or (X) has heat resistance, high transparency in the ultraviolet and visible light range, and 280 ° C. or less. It is excellent in that the dehydration ring closure rate is high.

（式中、Ｘは２価の有機基を示し、Ｒ²⁸及びＲ²⁹は各々独立に一価の有機基で、ｅ及びｆは各々独立に０〜４の整数である。）

(In the formula, X represents a divalent organic group, R ²⁸ and R ²⁹ are each independently a monovalent organic group, and e and f are each independently an integer of 0 to 4.)

（一般式（ＩＸ）、（Ｘ）中、Ｍは単結合又は２価の有機基を示し、Ｒ³⁰〜Ｒ³⁵は、一価の有機基であり、各々独立に水素又は炭素数１から６のアルキル基、ｇ、ｈはそれぞれ独立に１〜４の整数を表し、ｃ及びｄは各々独立に０〜４の整数を表す。）

(In the general formulas (IX) and (X), M represents a single bond or a divalent organic group, R ^{30 to} R ³⁵ represent a monovalent organic group, and each independently represents hydrogen or 1 to 6 carbon atoms. And g and h each independently represent an integer of 1 to 4, and c and d each independently represents an integer of 0 to 4.)

  Such dicarboxylic acids have an alicyclic structure represented by general formula (II) or (III) or (IV) or (V), and an adamantane structure represented by general formula (VI) or (VII). Examples thereof include compounds represented by the following general formula (XV).

（式中、Ｚは炭素数１〜６の炭化水素基である。）

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms.)

  As other dicarboxylic acids having an alicyclic structure, compounds represented by the following general formula (XVI) are also preferred.

  Further, preferred examples of the dicarboxylic acids having a structure represented by the general formula (VIII), (IX) or (X) include compounds represented by the following general formula (XVII).

（式中、Ｚは炭素数１〜６の炭化水素基である。Ｍは単結合又は２価の有機基であり、−ＣＨ₂−，−Ｃ（ＣＨ₃）₂−，−Ｏ−，−Ｓ−，−ＳＯ₂−，−ＣＯ−，−（ＣＦ₃）₂−等である。）

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms. M is a single bond or a divalent organic group, and —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, — S-, -SO _2- , -CO-,-(CF ₃ ) _2-, etc.)

  In the general formula (XVII), X is preferably a compound represented by the following general formula (XVIII).

（式中、ｎは１〜６の整数を表す。）

(In the formula, n represents an integer of 1 to 6.)

  The divalent organic group represented by V in the general formula (I) is the one of the above (UV5), specifically, the structure represented by the following general formula (XII) is heat resistant, i It is preferable since it exhibits line permeability and low residual stress.

（式中、Ｒ³⁸、Ｒ⁴³は各々独立に二価の有機基を表し、Ｒ³⁹〜Ｒ⁴²は各々独立に水素又は炭素数１から６のアルキル基である。ｍは１〜１００の整数を表す。）

(In the formula, R ³⁸ and R ⁴³ each independently represents a divalent organic group, R ^{39 to} R ⁴² each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms. M is an integer of 1 to 100. Represents.)

Examples of the divalent organic group of R ³⁸ and R ^{43 and} the monovalent organic group of R ^{39 to} R ⁴² include hydrocarbon groups having 1 to 10 carbon atoms (alkyl group, alkylene group, etc.), alkyl ether groups, and fluoroalkyl groups. Group, fluoroalkyl ether group, phenyl group and the like are preferable. The number m of repeating units is preferably 1 to 100.

  Examples of the dicarboxylic acid of X in the B structural unit include 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-bis (p-carboxyphenyl) propane, 5-tert- Aromatic dicarboxylic acids such as butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid are preferred. In addition, as the dicarboxylic acid of Z in the general formula (XIII), those exemplified above can be used. These compounds can be used alone or in combination of two or more.

  In the case of the polybenzoxazole precursor represented by the general formula (XIII), the divalent organic group represented by Y is generally derived from a diamine that reacts with a dicarboxylic acid to form a polyamide structure (however, It is a residue other than 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 Examples of aromatic diamine compounds such as-(4-aminophenoxy) phenyl] ether and 1,4-bis (4-aminophenoxy) benzene, and other diamines containing a silicone group include LP-7100, X-22 161AS, X-22-161A, X-22-16 1B, X-22-161C, and X-22-161E (all are trade names manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, but are not limited thereto. 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 photosensitive agent which is (b) component with the said polybenzoxazole precursor. The photosensitive agent has a function for a developer of a film formed from the composition in response to light. Although there is no restriction | limiting in particular in a photosensitive agent, It is preferable that it generates an acid or a radical by light.

  In the case of a positive type, it is more preferable that the acid is generated 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, and triarylsulfonium salts.

  In addition, when there is a group having a photocrosslinkable group such as acryloyl group or methacryloyl group in the structure of U, V, X, Y in the above general formula (I), (b) a component that generates a radical, That is, it can be used as a negative photosensitive resin composition by using a photopolymerization initiator. This is because it has a function of reducing the solubility of the light irradiated portion in the 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) is 5 with respect to 100 parts by weight of the component (a) from the viewpoint of the difference in dissolution rate between the exposed part and the unexposed part and the allowable range of sensitivity. -100 weight part is preferable, and 8-40 weight part is more preferable.

((C) component: solvent)
Examples of the solvent (c) used in the present invention include γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, and 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. 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) that generates an acid by heating 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, since the dehydration cyclization reaction can be further lowered by using a specific resin having a high dehydration ring closure rate of about 280 ° C. or less and a thermal acid generator according to the present invention, it can be cured even at low temperature. The physical properties of this film are comparable to those cured at high temperatures.

  The acid generated from the thermal acid generator is preferably a strong acid. Specifically, for example, p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, nonafluoro Perfluoroalkylsulfonic acid such as butanesulfonic acid, methanesulfonic acid, ethanesulfonic acid, alkylsulfonic acid such as butanesulfonic acid, and the like are preferable. 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, or 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 diaryliodonium salts such as diphenyliodonium salt, di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salt, trialkylsulfonium salts such as trimethylsulfonium salt, dimethyl A dialkyl monoarylsulfonium salt such as a phenylsulfonium salt, a diarylmonoalkyliodonium salt such as a diphenylmethylsulfonium salt, and the like are preferable. This is 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.

  In view of the above, the thermal acid generator as the onium salt includes, for example, arylsulfonic acid, camphorsulfonic acid, perfluoroalkylsulfonic acid or diaryliodonium salt of alkylsulfonic acid, di (alkylaryl) iodonium salt, 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.

  As the imide sulfonate, naphthoyl imide sulfonate is desirable. 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.

As the component (d), as shown in the following chemical formula (XIX), a compound having a structure of R ¹ R ² C═N—O—SO ₂ —R (1% weight loss temperature 204 ° C., 5% A weight reduction 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. R ¹ may be a cyano group, and R ² may be, for example, a methoxyphenyl group or a phenyl group.

また、上記（ｄ）成分として、下記の化学式（ＸＸ）に示すように、アミド構造−ＨＮ−ＳＯ₂−Ｒをもつ化合物（１％重量減少温度１０４℃、５％重量減少温度２７０℃）を用いることもできる。ここでＲとしては、例えば、メチル基、エチル基、プロピル基等のアルキル基、メチルフェニル基、フェニル基等のアリール基、トリフルオロメチル基、ノナフルオロブチル等のパーフルオロアルキル基などが挙げられる。また、−ＨＮ−ＳＯ₂−Ｒの結合する基としては、例えば、２，２,−ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパンや２，２,−ビス（４−ヒドロキシフェニル）プロパン、ジ（４−ヒドロキシフェニル）エーテル等が挙げられる。

Further, as the component (d), as shown in the following chemical formula (XX), a compound having an amide structure —HN—SO ₂ —R (1% weight reduction temperature 104 ° C., 5% weight reduction temperature 270 ° C.) It 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) 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.

  Component (d) is preferably blended in an amount of 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, and even more preferably 0.5 to 10 parts by weight per 100 parts by weight of component (a). .

[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 component (a) in an alkaline aqueous solution, for example, a compound having a phenolic hydroxyl group can be contained. When a compound having a phenolic hydroxyl group is added, the dissolution rate of the exposed area increases when developing with an aqueous alkaline solution, and the sensitivity increases, and the film is prevented from melting when the film is cured after pattern formation. be able to.

  Although there is no restriction | limiting in particular in the compound which has a phenolic hydroxyl group which can be used for this invention, Since the melt | dissolution promotion effect of an exposure part will become small when molecular weight becomes large, a compound with a molecular weight of 1,500 or less is generally preferable. For example, the compounds represented by the following general formula (XXI) are particularly preferable because they are excellent in the balance between the effect of promoting the dissolution of the exposed portion and the effect of preventing the melting of the film during curing.

（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、ｗ及びｘは各々独立に１又は２であり、ｙびｚは各々独立に０〜３の整数である。）

(In the formula, X represents a single bond or a divalent organic group, each R independently represents an alkyl group or an alkenyl group, w and x each independently represent 1 or 2, and y and z represent each independently. It is an integer of 0 to 3).

  The compounding amount 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 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 dissolution inhibitor is preferably 0.01 to 50 parts by weight, more preferably 0.01 to 30 parts by weight with respect to 100 parts by weight of the component (a), from the viewpoint of sensitivity and an allowable range of development time. 0.1-20 weight part is further more preferable.

((3) Adhesion imparting agent)
The photosensitive resin composition according to 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, urea propyltriethoxysilane, 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, isopropyldiphenylsilanol, 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 (butyldihi Loxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Benzene and the like. Examples of the aluminum chelate compound include tris (acetylacetonate) aluminum, acetylacetate aluminum diisopropylate, and the like.

  When using these adhesiveness imparting agents, the blending amount is preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of component (a).

((4) Surfactant or leveling agent)
Further, the photosensitive resin composition according to 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, and Megafax F171 is a commercially available product. F173, R-08 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC430, FC431 (trade name, manufactured by Sumitomo 3M), organosiloxane polymers KP341, KBM303, KBM403, KBM803 (manufactured by Shin-Etsu Chemical Co., Ltd.) Product name).

[Pattern manufacturing method]
Next, a pattern manufacturing method according to the present invention will be described. The method for producing a pattern of the present invention includes a step of applying the above-described photosensitive resin composition on a support substrate and drying, a step of exposing the photosensitive resin film obtained by the drying step to a predetermined pattern, A polybenzoxazole pattern can be obtained through a step of developing the exposed photosensitive resin film and a step of heat-treating the developed photosensitive resin film. Hereinafter, each step will be described.

(Coating / drying (film formation) process)
First, in the step of applying and drying the photosensitive resin composition on a support substrate, the above-described process is performed on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (for example, TiO ₂ , SiO ₂ ), or silicon nitride. The photosensitive resin composition is spin-coated using a spinner or the like and then dried using a hot plate, an oven, or the like. 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 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 pattern obtained after development is preferably subjected to heat treatment at a temperature of 120 to 300 ° C., thereby forming a heat-resistant polyoxazole pattern having an oxazole ring or other functional group. More preferably, the heat treatment step is performed at a temperature of 160 to 250 ° C. The heat treatment is preferably performed under nitrogen because the oxidation of the photosensitive resin film can be prevented. In this temperature range, cyclization dehydration occurs efficiently, and damage to the substrate and device is small. Therefore, by using the pattern manufacturing method of the present invention, the device can be obtained 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. Further, in US Pat. No. 5,739,915, when a polyimide precursor thin film is dehydrated and closed using microwaves, a method of avoiding damage to the polyimide thin film or the base material by irradiating with a frequency changed in a short period. Has been proposed.

  When microwaves are irradiated in pulses while changing the frequency, standing waves can be prevented and the substrate surface can be heated uniformly. Furthermore, if the substrate includes metal wiring, such as an electronic component, irradiating microwaves in a pulsed manner while changing the frequency can prevent discharge from the metal and protect the electronic component from destruction. 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.

  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 the polybenzoxazole precursor in the photosensitive resin composition of the present invention is dehydrated and cyclized is preferably turned on and 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 preferably about 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 is applied and dried by a spin coat method, light is irradiated from above 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 to form a pattern. To do. Thereafter, it is heated to form a polybenzoxazole film as the surface protective film layer 8 (fifth step, FIG. 5). This surface protective film layer (polybenzoxazole film) 8 protects the conductor layer from external stress, α rays, etc., 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 300 ° C. or higher, curing can be performed using low temperature heating of 280 ° C. or lower. Even at 280 ° C or lower, the photosensitive resin composition of the present invention undergoes sufficient cyclization dehydration reaction, so that its film 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 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 by this invention has the pattern formed by the manufacturing method of the said pattern using the photosensitive resin composition mentioned above. Here, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like. In particular, MRAM (Magnet Resistive Random Access Memory) having low heat resistance is preferable.

  Further, the pattern can be used specifically for forming a surface protective film or an interlayer insulating film of an electronic component such as a semiconductor device, an interlayer insulating film of a multilayer wiring board, or 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 Copolymer of Polybenzoxazole Precursor In a 0.5 liter flask equipped with a stirrer and a thermometer, 19.28 g of 1,4-cyclohexanedicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid After charging 23.61 g of acid and 133 g of N-methylpyrrolidone and cooling the flask to 5 ° C., 45.68 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of acid chloride. Next, 187 g of N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer, and 64.46 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After stirring and dissolving, 30.37 g of pyridine was added, and the acid chloride solution was added dropwise over 30 minutes while maintaining the temperature at 5 to 15 ° C., and then stirring was continued for 60 minutes. 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 (polybenzoxazole precursor) (hereinafter referred to as polymer I). The polymer I had a weight average molecular weight of 34,400 and a dispersity of 2.3 determined by GPC standard polystyrene conversion.

(Synthesis Example 2)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that 1,4-cyclohexanedicarboxylic acid used in Synthesis Example 1 was replaced with 1,3-phenylenediacetic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight of 28,000 and a dispersity of 1.4 determined by standard polystyrene conversion.

(Synthesis Example 3)
The synthesis was performed under the same conditions as in Synthesis Example 1, except that 1,4-cyclohexanedicarboxylic acid used in Synthesis Example 1 was replaced with 1,3-bis (carboxypropyl) tetramethyldisiloxane. The obtained polyhydroxyamide (hereinafter referred to as polymer III) had a weight average molecular weight of 28,000 and a dispersity of 1.4 determined by standard polystyrene conversion.

(Synthesis Example 4)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the molar ratio of 1,4-cyclohexanedicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid in Synthesis Example 1 was changed to 5: 1. The obtained polyhydroxyamide (hereinafter referred to as polymer IV) had a weight average molecular weight of 33,600 and a dispersity of 1.8 determined by standard polystyrene conversion.

(Synthesis Example 5)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that the molar ratio of 1,4-cyclohexanedicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid in Synthesis Example 1 was changed to 1: 5. The obtained polyhydroxyamide (hereinafter referred to as polymer V) had a weight average molecular weight of 39,000 and a dispersity of 1.9, as determined by standard polystyrene conversion.

(Synthesis Example 6)
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, 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 three times with pure water, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer VI). The weight average molecular weight calculated | required by standard polystyrene conversion was 17,900, and dispersion degree was 1.5.

(Synthesis Example 7)
The 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane used in Synthesis Example 6 was replaced with the same molar amount of 2,2′-bis (3-amino-4-hydroxyphenyl) sulfone. Except for the above, synthesis was performed under the same conditions as in Synthesis Example 1. The obtained polyhydroxyamide (hereinafter referred to as polymer VII) had a weight average molecular weight of 21,600 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Synthesis Example 8)
The synthesis was carried out under the same conditions as in Synthesis Example 1 except that 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 6 was replaced with the same molar amount of isophthalic acid. The resulting polyhydroxyamide (hereinafter referred to as polymer VIII) had a weight average molecular weight of 13,700 and a dispersity of 1.5 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 1-5 and Comparative Examples 1-3
A resin solution prepared by dissolving 10.0 g of the polybenzoxazole precursor obtained in Synthesis Examples 1 to 8 in 15 g of N-methylpyrrolidone was spin-coated on a silicon wafer, dried at 120 ° C. for 3 minutes, and a film thickness of 12 μm. A coating film (A) was obtained. This coating film was heated in an inert gas oven 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 film (B) heated at 200 ° C., A cured film (C) heated at 350 ° C. was 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 (manufactured by Shimadzu Corporation) was used as a measuring device. 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%.

In addition, the dehydration ring closure rate of the structural unit having a specific skeleton in the present invention in the polybenzoxazole precursor copolymer, that is, the polybenzoxazole precursor alone (A structural unit of the general formula (I)) is also shown in the examples. It calculated | required similarly about 1-5.
Table 1 shows the dehydration ring closure rate of the polymers obtained as described above.

  From the above results, in the polymers of Examples 1 to 5, the dehydration ring closure rate at 200 ° C. exceeded 30% and reached nearly 60%, which was higher than 20% to 26% in Comparative Examples 1 to 3.

Examples 6 to 10 and Comparative Examples 4 and 5
(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 Table 2, NMP represents N-methylpyrrolidone. 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 to D3 are compounds represented by the following chemical formulas (XXII) and (XXIII), respectively.

  The obtained photosensitive resin composition solution is spin-coated on a silicon wafer to form a coating film having a dry film thickness of 3 to 10 μm, and then i-line (using an ultrahigh pressure mercury lamp through an interference filter) 365 nm) exposure. 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.

  Further, 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 at 150 ° C. for 30 minutes in a nitrogen atmosphere, and further heated at 320 ° C. for 1 hour or 200 ° C. for 1 hour to obtain a cured film. Next, this cured film was peeled off using an aqueous hydrofluoric acid solution, washed with water, dried, and then examined for film properties such as glass transition point (Tg), elongation (measured with a tensile tester), and 5% weight loss temperature. Further, the dehydration ring closure rate was measured by the same method as described above. These measurement results are shown in Table 4.

As described above, the photosensitive resin composition of the present invention has high sensitivity and can form a pattern with high resolution. Further, as shown in Table 4, even in the case of Tg, elongation, and curing at 200 ° C., film properties comparable to those when cured at 320 ° C. were obtained.
The 5% weight loss temperature was slightly lower when cured at 200 ° C. than when cured at 320 ° C., but was higher than 300 ° C. compared to the comparative example.

Regarding the dehydration ring closure rate, when cured at 200 ° C. in the examples, it was already as high as 90% or more. On the other hand, in the case of curing at 200 ° C. in the comparative example, the case where the dehydration cyclization rate was around 50% was included, the results varied and the progress of the cyclization dehydration reaction was insufficient.
As described above, the photosensitive resin composition of the present invention is excellent in sensitivity, resolution, and adhesiveness, and also has excellent heat resistance even when used in a low-temperature curing process. It is particularly suitable for the manufacture of MRAM and the like that require low temperature curing.

  Next, a thermal acid generator as a component (d) was further blended in the solutions of the photosensitive resin compositions prepared in Examples 6 to 10 as shown in Table 5. In Table 5, the compounds represented by the following chemical formula (XXIV) were used for d1 to d4 of the component (d). Then, the dehydration ring closure rate when thermosetting at 200 ° C. and 180 ° C. for 1 hour was measured in the same manner as in Example 1. The results are also shown in Table 5.

  As is clear from Table 5, by using a thermal acid generator in combination, the dehydration cyclization rate is greatly increased even when cured at 180 ° C. compared to the case where no addition is made, and a high cyclization rate can be obtained even at a lower temperature. It was.

  As described above, the photosensitive resin composition according to the present invention uses a polybenzoxazole photosensitive resin film having a specific structural unit having a high dehydration ring closure rate even at a low temperature as a base resin, so that physical properties of the film after curing are obtained. Performance comparable to that cured at high temperatures. In addition, according to the method for producing a pattern of the present invention, the use of the composition makes it possible to obtain a pattern having a good shape with excellent sensitivity, resolution and adhesiveness, excellent heat resistance even in a low temperature curing process, and low water absorption. can get. Since it has a good shape, a pattern excellent in adhesiveness, and heat resistance, and can be cured by a low-temperature process, damage to the device can be avoided and a highly reliable electronic component can be obtained. Therefore, it 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 (11)

(A) the following general formula comprising and an A structural unit B structural units represented by (I) polybenzoxazole precursor copolymer, and (b) a photosensitive agent, and (c) a solvent A photosensitive resin composition characterized by comprising.

[In the formula, U, V, W, and X represent divalent organic groups, and U and W are different groups or V and X are different groups, or both U and W, and V and X are both J and k represent the mole fractions of the A structural unit and the B structural unit, respectively, the sum of j and k is 100 mol%, and the V is represented by the following general formula (IX), It is a group represented by either (X) or (XII) . ]

(In the general formulas (IX) and (X), M represents a single bond or a divalent organic group, and R ^{30 to} R ³⁵ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or a monovalent organic group. And g and h each independently represent an integer of 1 to 4, and c and d each independently represents an integer of 0 to 4.)

(In General Formula (XII), R ³⁸ and R ⁴³ are each independently a divalent organic group, R ^{39 to} R ⁴² are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and m is 1 to 100. Represents an integer.)   The component (a) is a copolymer of a polybenzoxazole precursor composed of an A structural unit and a B structural unit represented by the general formula (I), and j and k in the general formula (I) are each an A structure. The mole fraction of units and B structural units is shown, the sum of j and k is 100 mol%, j is in the range of 1 to 99 mol%, and k is in the range of 1 to 99 mol%. 2. The photosensitive resin composition according to 1. In the general formula (I) of the component (a), the sum of j and k is 100 mol%, j is in the range of 5 to 85 mol%, and k is in the range of 15 to 95 mol%. Item 3. The photosensitive resin composition according to Item 1 or 2 . The photosensitive resin composition according to any one of claims 1 to 3 , wherein the component (b) is a photosensitive agent that generates an acid or a radical by light. The photosensitive resin composition according to any one of claims 1 to 4 , further comprising a thermal acid generator that generates an acid by heating as the component (d). A polybenzoxazole film formed by using the photosensitive resin composition according to any one of claims 1 to 5 and dehydrating and ring-closing the polybenzoxazole precursor. The process of apply | coating the photosensitive resin composition of any one of Claims 1-5 on a support substrate, and drying, and exposing the photosensitive resin film obtained by the said drying to a predetermined pattern And a step of developing the photosensitive resin film after exposure using an alkaline aqueous solution, and a step of heat-treating the photosensitive resin film after development. 8. The method for producing a pattern according to claim 7 , wherein in the step of heat-treating the photosensitive resin film after development, the heating step irradiates the microwave in a pulsed manner while changing the frequency. The method for producing a pattern according to claim 7 or 8 , wherein in the step of heat-treating the photosensitive resin film after development, the heat-treatment temperature is 280 ° C or lower. An electronic component comprising a layer having a pattern obtained by the method for producing a pattern according to any one of claims 7 to 9 as an interlayer insulating film layer and / or a surface protective film layer. The electronic component according to claim 10 , wherein the electronic component is a magnetoresistive memory.

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