JP4639956B2 - Photosensitive resin composition, pattern manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to a photosensitive resin composition containing a polybenzoxazole precursor and excellent in heat resistance, a method for producing a pattern using the 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, if this is used, the pattern production 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. In the negative type, 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, see Patent Documents 5 to 10) ), A self-sensitized polyimide having a 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 type requires an organic solvent such as N-methylpyrrolidone for development, a positive photosensitive resin that can be developed with an aqueous alkaline solution has recently been proposed. In the positive type, a method in which an o-nitrobenzyl group is introduced into a polyimide precursor via an ester bond (for example, see Non-Patent Document 1), a method in which a naphthoquinonediazide compound is mixed in a soluble hydroxylimide or polyoxazole precursor (for example, Patent Documents 13 and 14), a method of introducing naphthoquinone diazide into a soluble polyimide via an ester bond (for example, see Non-Patent Document 2), and a method in which naphthoquinone diazide is mixed into a polyimide precursor (for example, see Patent Document 15) and so on.
However, the negative type has a problem in resolution due to its function, and in some applications, the yield in manufacturing is reduced. In addition, since the structure of the polymer to be used is limited in the above, the physical properties of the finally obtained film are limited, which is not suitable for multipurpose use. On the other hand, the positive type 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) can be mentioned. The deterioration of the induced film characteristics, which are excellent in the film characteristics, show a decrease in sensitivity due to insufficient solubility due to the high molecular weight, and it is difficult to say that both are materials at a 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 56-38038 A JP 59-108031 A JP 59-220730 A JP 59-232122 A Japanese Unexamined Patent Publication No. 60-6729 JP-A-60-72925 JP-A-61-57620 JP 59-219330 A JP-A-231533 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 (Magnetic 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 less, as well as the conventional high temperature of about 350 ° C., and the physical properties of the film after curing are cured at a high temperature. Buffer coating materials that can provide incomparable performance have become essential.
Therefore, the present invention relates to a photosensitive polybenzoxazole precursor that can be developed with an alkali, by using a specific resin having a high dehydration ring closure rate at about 280 ° C. or less, so that a cured film at a high temperature can be obtained even at a low temperature. It is intended to provide a photosensitive resin composition having high heat resistance that is not different from the physical properties of the above. In addition, the present invention is a pattern that can be developed with an alkaline aqueous solution by using the above composition, has excellent sensitivity and resolution, and has excellent heat resistance by a low-temperature curing process at 280 ° C. or less, whereby a pattern with a good shape can be obtained. A manufacturing method is provided.
In addition, the present invention provides a highly reliable electronic component with a high yield by avoiding damage to the device by having a pattern with a good shape and characteristics and being cured by a low temperature process.

The present invention relates to the following.
[1] A photosensitive resin composition comprising (a) a polybenzoxazole precursor having a repeating unit represented by formula (I), (b) a photosensitive agent, and (c) a solvent.

［一般式（Ｉ）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］
（ＵＶ１）：炭素数６〜２０の脂環の構造を含む基、
（ＵＶ２）：

[In General Formula (I), U or V represents a divalent organic group, and at least one of U or V is any one of groups including structures represented by (UV1) to (UV5) shown below. ]
(UV1): a group containing an alicyclic structure having 6 to 20 carbon atoms,
(UV2):

（但し、Ｘは２価の有機基である）で表される構造を含む基、
（ＵＶ３）：

A group containing a structure represented by the formula (where X is a divalent organic group):
(UV3):

（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、ｌは０又は１である）で表される構造を含む基、
（ＵＶ４）：

Wherein R is 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 l is 0 Or a group having a structure represented by 1),
(UV4):

（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、
（ＵＶ５）：

Wherein R is independently a hydrogen atom or a monovalent organic group, and n represents an integer of 1 to 6,
(UV5):

（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
［２］ （ａ）成分の一般式（Ｉ）中、Ｕ又はＶの少なくとも一方が、一般式（ＩＩ）、（ＩＩＩ）、（ＩＶ）または（Ｖ）で表される、炭素数６〜２０の脂環の構造を含む２価の有機基である上記［１］に記載の感光性樹脂組成物。

(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 [2] In the general formula (I) of the component (a), at least one of U or V is represented by the general formula (II), (III), (IV) or (V), and has 6 to 6 carbon atoms. The photosensitive resin composition according to the above [1], which is a divalent organic group containing 20 alicyclic structures.

（一般式（ＩＩ）、（ＩＩＩ）、（ＩＶ）、（Ｖ）中、Ｒ^１からＲ^２１は、各々独立に水素または炭素数１〜６のアルキル基であり、ｈ、ｉ、ｊ、ｋ、ｐ、ｑ、ｒは、各々独立に１〜６の整数を表す）
［３］ （ａ）成分のＵ又はＶの少なくとも一方が、脂環の骨格として、アダマンタン構造を有する［１］に記載の感光性樹脂組成物。
［４］ （ａ）成分の一般式（Ｉ）中、Ｕ又はＶの少なくとも一方が、一般式（ＶＩ）または（ＶＩＩ）で表される上記［３］に記載の感光性樹脂組成物。

(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 h, i, j, k , P, q and r each independently represents an integer of 1 to 6)
[3] The photosensitive resin composition according to [1], wherein at least one of component U or V has an adamantane structure as an alicyclic skeleton.
[4] The photosensitive resin composition according to the above [3], wherein in the general formula (I) of the component (a), at least one of U or V is represented by the general formula (VI) or (VII).

（一般式（ＶＩ）、（ＶＩＩ）中、Ｒ^２２からＲ^２７は、各々独立に水素または炭素数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。）
［５］ （ａ）成分の一般式（Ｉ）中、Ｖが、下記一般式（ＶＩＩＩ）で表される上記［１］に記載の感光性樹脂組成物。

(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) .)
[5] The photosensitive resin composition according to the above [1], wherein V is represented by the following general formula (VIII) in the general formula (I) of the component (a).

（一般式（ＶＩＩＩ）中、Ｘは２価の有機基を示し、Ｒ^２８及びＲ^２９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。）
［６］ （ａ）成分の一般式（Ｉ）中、Ｖが、下記一般式（ＩＸ）または（Ｘ）で表される上記［１］に記載の感光性樹脂組成物。

(In general formula (VIII), 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.)
[6] The photosensitive resin composition according to the above [1], wherein in general formula (I) of component (a), V is represented by the following general formula (IX) or (X).

（一般式（ＩＸ）、（Ｘ）中、Ｍは単結合または２価の有機基を示し、Ｒ^３０〜Ｒ^３５は各々独立に水素、炭素数１から６のアルキル基であり、Ｒ^３０〜Ｒ^３５は各々独立に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。）
［７］ （ａ）成分の一般式（Ｉ）中、Ｕが一般式（ＸＩ）で表される上記［１］に記載の感光性樹脂組成物。

(In the general formula (IX), (X), M represents a single bond or a divalent organic ^group, an alkyl group of R 30 ^{to R 35} are each independently hydrogen, a carbon number of 1 to ^{6, R 30} ~ R ³⁵ is each independently a monovalent organic group, 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.)
[7] The photosensitive resin composition according to the above [1], wherein U is represented by the general formula (XI) in the general formula (I) of the component (a).

（一般式（ＸＩ）中、Ｒ^３６、Ｒ^３７は各々独立に水素または炭素数１から６のアルキル基であり、ｎは１〜６の整数を表す。）
［８］ （ａ）成分の一般式（Ｉ）中、Ｖが一般式（ＸＩＩ）で表される上記［１］に記載の感光性樹脂組成物。

(In General Formula (XI), 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)
[8] The photosensitive resin composition according to the above [1], wherein V is represented by the general formula (XII) in the general formula (I) of the component (a).

（一般式（ＸＩＩ）中、Ｒ^３８、Ｒ^４３は各々独立に二価の有機基、Ｒ^３９〜Ｒ^４２は各々独立に水素または炭素数１から６のアルキル基である。ｍは１〜１００の整数を表す。）
［９］ 前記（ｂ）成分が、光により酸又はラジカルを発生するものである上記［１］〜［８］のいずれかに記載の感光性樹脂組成物。
［１０］ さらに（ｄ）成分として加熱により酸を発生する熱酸発生剤を上記［１］〜［９］のいずれかに記載の感光性樹脂組成物。
［１１］ ［１］〜［１０］のいずれかに記載の感光性樹脂組成物を用い、そのポリベンゾオキサゾール前駆体を脱水閉環して形成されるポリベンゾオキサゾール膜。
［１２］ ［１］〜［１０］のいずれかに記載の感光性樹脂組成物を支持基板上に塗布し乾燥する工程と、前記乾燥により得られた感光性樹脂膜を所定のパターンに露光する工程と、前記露光後の感光性樹脂膜をアルカリ水溶液を用いて現像する工程と、前記現像後の感光性樹脂膜を加熱処理する工程とを含むパターンの製造方法。
［１３］ 前記現像後の感光性樹脂膜を加熱処理する工程において、その加熱工程がマイクロ波を周波数を変化させながらパルス状に照射するものであることを特徴とする上記［１２］に記載のパターンの製造方法。
［１４］ 前記現像後の感光性樹脂膜を加熱処理する工程において、その加熱処理温度が２８０℃以下であることを特徴とする上記［１２］又は上記［１３］に記載のパターンの製造方法。
［１５］ 上記［１２］、［１３］又は上記［１４］に記載のパターンの製造方法により得られるパターンの層を、層間絶縁膜層及び／又は表面保護膜層として有する電子部品。
［１６］ 電子部品が、磁気抵抗メモリ（ＭＲＡＭ（Ｍａｇｎｅｔ Ｒｅｓｉｓｔｉｖｅ Ｒａｎｄｏｍ Ａｃｃｅｓｓ Ｍｅｍｏｒｙ））である上記［１５］に記載の電子部品。

(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. M is 1 to 100. Represents an integer.)
[9] The photosensitive resin composition according to any one of [1] to [8], wherein the component (b) generates an acid or a radical by light.
[10] The photosensitive resin composition according to any one of [1] to [9], wherein a thermal acid generator that generates an acid by heating is further used as the component (d).
[11] A polybenzoxazole film formed by using the photosensitive resin composition according to any one of [1] to [10] and dehydrating and ring-closing the polybenzoxazole precursor.
[12] A step of applying and drying the photosensitive resin composition according to any one of [1] to [10] on a support substrate, and exposing the photosensitive resin film obtained by the drying to a predetermined pattern The manufacturing method of the pattern including the process, The process of developing the photosensitive resin film after the said exposure using alkaline aqueous solution, and the process of heat-processing the photosensitive resin film after the said image development.
[13] The process according to [12], 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. Pattern manufacturing method.
[14] The process for producing a pattern as described in [12] or [13], wherein the heat treatment temperature is 280 ° C. or lower in the step of heat-treating the photosensitive resin film after development.
[15] An electronic component having a pattern layer obtained by the pattern production method according to [12], [13] or [14] as an interlayer insulating film layer and / or a surface protective film layer.
[16] The electronic component according to [15], wherein the electronic component is a magnetoresistive memory (MRAM (Magnetic Resistive Random Access Memory)).

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. By using a specific polybenzoxazole photosensitive resin film having a high dehydration cyclization rate even at 280 ° C. or lower as a base resin, a performance comparable to that obtained by curing the film at a high temperature can be obtained. 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 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.
In addition, 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, the yield is high because there is little damage to the device.

Hereinafter, embodiments of the present invention will be described.
In the present invention, a polybenzoxazole precursor having a repeating unit represented by the general formula (I) is used as the component (a).

［一般式（Ｉ）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］
（ＵＶ１）：炭素数６〜２０の脂環の構造を含む基、
（ＵＶ２）

[In General Formula (I), U or V represents a divalent organic group, and at least one of U or V is any one of groups including structures represented by (UV1) to (UV5) shown below. ]
(UV1): a group containing an alicyclic structure having 6 to 20 carbon atoms,
(UV2)

（但し、Ｘは２価の有機基である）で表される構造を含む基、
（ＵＶ３）：

A group containing a structure represented by the formula (where X is a divalent organic group):
(UV3):

（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、ｌは０又は１である）で表される構
造を含む基、
（ＵＶ４）：

Wherein R is 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 l is 0 Or a group having a structure represented by 1),
(UV4):

（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、
（ＵＶ５）：

Wherein R is independently a hydrogen atom or a monovalent organic group, and n represents an integer of 1 to 6,
(UV5):

（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

(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). Base

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

The polybenzoxazole precursor used in the present invention has a repeating unit represented by the above general formula (I), but its solubility in an alkaline aqueous solution is derived from an OH group (generally a phenolic hydroxyl group) bonded to U. Therefore, it is preferable that the amide unit containing the OH group is contained in a certain ratio or more.
For example, the following general formula (A)

（一般式（Ａ）中、Ｕは２価の有機基を示し、ＶとＷは２価の有機基を示す。ｊとｋは、それぞれの繰り返し単位のモル分率を示し、ｊとｋの和は１００モル％であり、ｊが６０〜１００モル％、ｋが４０〜０モル％である）で表されるポリイミド前駆体であることが好ましい。ここで、式中のｊとｋのモル分率は、ｊ＝８０〜１００モル％、ｋ＝２０〜０モル％であることがより好ましい。

(In general formula (A), U represents a divalent organic group, V and W represent a divalent organic group. J and k represent the mole fraction of each repeating unit, and The sum is 100 mol%, and j is preferably 60 to 100 mol% and k is 40 to 0 mol%). Here, the molar fraction of j and k in the formula is more preferably j = 80 to 100 mol% and k = 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.

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 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 formula (I) will be described in detail.
First, a group preferable as U will be described.
(UV1) The group containing an alicyclic structure having 6 to 20 carbon atoms may be present as U or V in the general formula (I). The group containing an alicyclic skeleton is a group containing an alicyclic structure or an adamantane structure represented by the general formula (II), (III), (IV) or (V). It is preferable because it has transparency in the visible light range and is excellent in terms of high dehydration ring closure at 280 ° C. or lower. The group containing an adamantane structure is preferably a group represented by the general formula (VI) or (VII).

（一般式（ＩＩ）、（ＩＩＩ）、（ＩＶ）、（Ｖ）中、Ｒ^１からＲ^２１は、各々独立に水素または炭素数１〜６のアルキル基であり、ｈ、ｉ、ｊ、ｋ、ｐ、ｑ、ｒ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 h, i, j, k , P, q and r each independently represents an integer of 1 to 6.)

（一般式（ＶＩ）、（ＶＩＩ）中、Ｒ^２２からＲ^２７は、各々独立に水素または炭素数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 the group described as (UV4) (preferably a group represented by the general formula (XI), for example, an alkylene group or an alkylidene group) has a U structure, it has heat resistance, transparency in the ultraviolet and visible light range. It is excellent in that it has a high dehydration ring closure rate at 280 ° C. or lower.

（一般式（ＸＩ）中、Ｒ^３６、Ｒ^３７は各々独立に水素または炭素数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。）

(In General Formula (XI), R ³⁶ and R ³⁷ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms. N represents an integer of 1 to 6)

  Examples of the diamines as described above include

（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。）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).

Other diamines include 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 ( Aromatic diamines other than those described above, such as 4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, are included, but not limited thereto. . These diamines can be used alone or in combination of two or more.
In addition, when using the diamine which has the said alicyclic structure, an adamantane structure, an alkylene group, etc., it is also possible to use together said other diamine to such an extent that the effect of this invention is not impaired.

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-described (UV1) alicyclic skeleton having 6 to 20 carbon atoms, specifically, the general formula (II), (III), (IV) or ( Examples thereof include an alicyclic structure represented by V) and an adamantane structure represented by the general formula (VI) or (VII).
The groups described as (UV2), (UV3), and (UV5) are also effective as V.
Specifically, the structure represented by the general formula (VIII) or (IX) or (X) has heat resistance, high transparency in the ultraviolet and visible light range, and a dehydration ring closure rate at 280 ° C. or lower. Is excellent in terms of high.

（一般式（ＶＩＩＩ）中、Ｘは２価の有機基を示し、Ｒ^２８及びＲ^２９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 general formula (VIII), 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は単結合または２価の有機基を示し、Ｒ^３０〜Ｒ^３５は、一価の有機基であり、各々独立に水素または炭素数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。）
このようなジカルボン類として、一般式（ＩＩ）または（ＩＩＩ）または（ＩＶ）または（Ｖ）で表される脂環式構造、一般式（ＶＩ）または（ＶＩＩ）で表されるアダマンタン構造を有するものとしては、

(In the general formulas (IX) and (X), M represents a single bond or a divalent organic group, R ^{30 to} R ³⁵ are monovalent organic groups, 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). As a thing,

（式中Ｚは炭素数１〜６の炭化水素基）が挙げられ、
その他の脂環構造を有するジカルボン酸としては

(Wherein Z is a hydrocarbon group having 1 to 6 carbon atoms),
Other dicarboxylic acids having an alicyclic structure

等も好ましいものとして挙げられる。
また、一般式（ＶＩＩＩ）、（ＩＸ）または（Ｘ）で表される構造を有するジカルボン酸類としては、

Are also preferred.
In addition, as dicarboxylic acids having a structure represented by the general formula (VIII), (IX) or (X),

式中Ｚは炭素数１〜６の炭化水素基である。また、Ｍは単結合または２価の有機基であり、−ＣＨ_２−，−Ｃ（ＣＨ_３）_２−，−Ｏ−，−Ｓ−，−ＳＯ_２−，−ＣＯ−，−（ＣＦ_３）_２−等が好ましいものとして挙げられる。
式中Ｘは

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. are mentioned as a preferable thing.
Where X is

（ｎは１〜６の整数を表す。）等が好ましいものとして挙げられる。

(N represents an integer of 1 to 6) and the like.

  In the present invention, 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 general formula (XII) is heat resistant, i-line It exhibits permeability and low residual stress, which is preferable.

（一般式（ＸＩＩ）中、Ｒ^３８、Ｒ^４３は各々独立に二価の有機基、Ｒ^３９〜Ｒ^４２は各々独立に水素または炭素数１から６のアルキル基である。ｍは１〜１００の整数を表す。
）
Ｒ^３８，Ｒ^４３の二価の有機基、Ｒ^３９〜Ｒ^４２の一価の有機基としては、炭素数１〜１０の炭化水素基（アルキル基、アルキレン基など）、アルキルエーテル基、フルオロアルキル基、フルオロアルキルエーテル基およびフェニル基等が好ましいものとして挙げられる。繰返し単位数ｍとしては１〜１００が好ましい。

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

  Other dicarboxylic acids 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-butylisophthalic acid, 5 -Aromatic dicarboxylic acids such as bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid and 2,6-naphthalenedicarboxylic acid can be used in combination. 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 (A), the divalent organic group represented by W 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. W 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 161B, X-22-161C, and X-22-161E (both Shin-Etsu Chemical Co., Ltd., trade name) does not but like limited thereto. These compounds are used alone or in combination of two or more.

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.

When there is a group having a photocrosslinkable group such as an acryloyl group or a methacryloyl group in the structure of U or V in the general formula (I), a component that generates a radical, that is, a photopolymerization initiator is used as the component (b). By using it, it can be used as a negative photosensitive resin composition. This 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) 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.

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 is generally adjusted so that the ratio of the solvent in the composition is 20 to 90% by weight.

  In the present invention, when a thermal acid generator that generates an acid by heating is used as the component (d), the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor is efficiently used as a catalyst for cyclization by causing a dehydration reaction. It is preferable because it works. By using together with a specific resin having a high degree of dehydration ring closure at about 280 ° C. or less according to the present invention, the dehydration cyclization reaction can be further lowered, so that the properties of the film after curing can be improved even at low temperature. Performance comparable to that of the cured product is obtained.

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 serve as a catalyst for the cyclization of the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor that causes a dehydration reaction. On the other hand, acid generators that generate hydrochloric acid, bromic acid, iodic acid, and nitric acid have weak acidity and are likely to volatilize by heating. 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.

From the above points, the thermal acid generator as an onium salt includes, for example, aryl sulfonic acid, camphor sulfonic acid, perfluoroalkyl sulfonic acid or diaryl iodonium salt of alkyl sulfonic 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.

In addition, as the component (d), as shown in the following chemical formula, a compound having a structure of R ¹ R ² C═N—O—SO ₂ —R (1% weight reduction temperature 204 ° C., 5% weight reduction temperature) 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.

また、上記（ｄ）成分として、下記、化学式に示すように、アミド構造−ＨＮ−ＳＯ_２−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−ＳＯ_２−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。

As the component (d), a compound having an amide structure —HN—SO ₂ —R (1% weight reduction temperature 104 ° C., 5% weight reduction temperature 270 ° C.) may be used as shown in the chemical formula below. it can. 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.

また、本発明で用いる（ｄ）成分としては、オニウム塩以外の強酸と塩基から形成された塩を用いることもできる。上記、強酸としては、例えば、ｐ−トルエンスルホン酸、ベンゼンスルホン酸のようなアリールスルホン酸、カンファースルホン酸、トリフルオロメタンスルホン酸、ノナフルオロブタンスルホン酸のようなパーフルオロアルキルスルホン酸、メタンスルホン酸、エタンスルホン酸、ブタンスルホン酸のようなアルキルスルホン酸が好ましい。塩基としては、例えば、ピリジン、２，４，６−トリメチルピリジンのようなアルキルピリジン、２−クロロ−Ｎ−メチルピリジンのようなＮ−アルキルピリジン、ハロゲン化−Ｎ−アルキルピリジン等が好ましい。さらに具体的には、ｐ−トルエンスルホン酸のピリジン塩（１％重量減少温度１４７℃、５％重量減少温度１９０℃）、ｐ−トルエンスルホン酸のＬ−アスパラギン酸ジベンジルエステル塩（１％重量減少温度２０２℃、５％重量減少温度２１８℃）、ｐ−トルエンスルホン酸の２，４，６−トリメチルピリジン塩、ｐ−トルエンスルホン酸の１，４−ジメチルピリジン塩などが保存安定性、現像性の点から好ましいものとして挙げられる。これらも２８０℃以下でのポリベンゾオキサゾール前駆体の環化脱水反応に際して分解し、触媒として働くことができる。
（ｄ）成分の配合量は、（ａ）成分１００重量部に対して０．１〜３０重量部が好まし
く、０．２〜２０重量部がより好ましく、０．５〜１０重量部がさらに好ましい。

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 the strong acid include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid such as nonafluorobutanesulfonic acid, and methanesulfonic acid. Alkyl sulfonic acids such as ethane sulfonic acid and butane sulfonic acid 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). .

In this invention, the compound which has the phenolic hydroxyl group which further promotes the solubility with respect to the aqueous alkali solution of (a) component can be 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.
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, generally a compound with a molecular weight of 1,500 or less is preferable. For example, the compounds represented by the following general formula (XIII) are particularly preferable because they are excellent in the balance between the effect of promoting dissolution of the exposed area and the effect of preventing melting during curing of the film.

（一般式（ＸＩＩＩ）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）
フェノール性水酸基を有する化合物の成分の配合量は、現像時間と、未露光部残膜率の許容幅の点から、（ａ）成分１００重量部に対して１〜３０重量部が好ましく、３〜２５重量部がより好ましい。

(In General Formula (XIII), X represents a single bond or a divalent organic group, each R independently represents an alkyl group or an alkenyl group, m and n each independently represent 1 or 2, p and q is each independently 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.

In this invention, the compound which inhibits the solubility with respect to the aqueous alkali solution of (a) component can further be 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 components 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 component (a) from the viewpoint of sensitivity and an allowable range of development time. More preferably, it is 1 to 20 parts by weight.

  The photosensitive resin composition of the present invention can contain an organic silane compound, an aluminum chelate compound and the like 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 adhesion grant agents, 0.1-30 weight part is preferable with respect to 100 weight part of (a) component, and 0.5-20 weight part is more preferable.

  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, and Megafax F171 is a commercially available product. , F173, R-08 (Dainippon Ink Chemical Co., Ltd. product name), Florard FC430, FC431 (Sumitomo 3M Co., Ltd. product name), Organosiloxane polymer KP341, KBM303, KBM403, KBM803 (Product made by Shin-Etsu Chemical Co., Ltd.) Name).

The photosensitive resin composition of this invention can be made into the pattern of polybenzoxazole through the process of apply | coating and drying on a support substrate, the process of exposing to a predetermined pattern, the process of developing, and the process of heat-processing. In the step of applying and drying on a support substrate, the photosensitive resin composition is applied to a spinner or the like on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO ₂ ), or silicon nitride. After spin coating using, it is dried using a hot plate, oven or the like.
Next, in the exposure step, the photosensitive resin composition formed as a film on the support substrate is irradiated with actinic rays such as ultraviolet rays, visible rays, and radiations through a mask. In the development process, the pattern is obtained by removing the exposed portion 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.
Next, in the heat treatment step, the obtained pattern is preferably subjected to a heat treatment at 120 to 300 ° C. to form a heat-resistant polyoxazole pattern having an oxazole ring or other functional groups. The heat treatment step is more preferably 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 saving 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 and device at, for example, 220 ° C. or lower.
For example, in Japanese Patent No. 2587148 and Japanese Patent No. 3031434, dehydration and ring closure of a polyimide precursor using a microwave is 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 the form of pulses while changing the frequency, standing waves can be prevented and the substrate surface can be heated uniformly. Furthermore, when the substrate includes metal wiring like an electronic component, it is possible to prevent the occurrence of electric discharge from the metal and to protect the electronic component from destruction by irradiating the microwave in pulses while changing the frequency. This is preferable.
The frequency of the microwave irradiated when dehydrating and cyclizing the polybenzoxazole precursor in the photosensitive resin composition of the present invention is in the range of 0.5 to 20 GHz, but is practically 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.
Although 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, it 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 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 is likely 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.
The photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, surface protective films and interlayer insulating films of semiconductor devices, interlayer insulating films of multilayer wiring boards It can be used for the formation of etc. The semiconductor device of the present invention is not particularly limited except that it has a surface protective film and an interlayer insulating film formed using the composition, and can have various structures.

An example of a manufacturing process of a semiconductor device which is an electronic component of the present invention will be described below. FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure. A series of steps from the first step to the fifth step is shown from the top to the bottom. In FIG. 1, a semiconductor substrate 1 such as a Si substrate having circuit elements is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. Has been. A film of polyimide resin or the like as the interlayer insulating film layer 4 is formed on the semiconductor substrate by a spin coat method or the like (first step).
Next, a photosensitive resin layer 5 such as chlorinated rubber or phenol novolac is formed on the interlayer insulating film layer 4 by spin coating, and a predetermined portion of the interlayer insulating film layer 4 is exposed by a known photolithography technique. Thus, a window 6A is provided (second step). The interlayer insulating film layer 4 of 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).
Furthermore, 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). 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 FIG. 1, the surface protective film is coated with the photosensitive resin composition by a spin coat method, dried, irradiated with light from a mask on which a pattern for forming a window 6C is formed at a predetermined portion, and then alkali. A pattern is formed by developing with an aqueous solution. After that, it is heated to form a surface protective film layer (polybenzoxazole film) 8 (fifth step). 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 heating at a low temperature of 280 ° C. or lower. 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 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.
As an electronic component having an electronic device having a surface protective film, an interlayer insulating film and the like obtained by using the photosensitive resin composition of the present invention, for example, MRAM (Magnetic Resistive Random Access Memory) having low heat resistance is used. ) Is preferred. Therefore, the photosensitive resin composition of the present invention is suitable for a surface protective film of MRAM.

Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited to the following Example.
Synthesis Example 1 Synthesis of Polybenzoxazole Precursor 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. After cooling to 5 ° C., 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 12.92 g of 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was added. After adding and dissolving with stirring, 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, and then stirring was continued for 30 minutes. It was. 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 weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer I was 13700, and dispersion degree was 1.4.

(Synthesis Example 2)
Synthesis Example 1 except that 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene used in Synthesis Example 1 was replaced with 1,1′-bis (3-amino-4-hydroxyphenyl) cyclohexane The synthesis was carried out under the same conditions as above. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight of 9700 and a dispersity of 1.3 determined by standard polystyrene conversion.

(Synthesis Example 3)
Synthesis Example 1 except that 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene used in Synthesis Example 1 was replaced with 2,2′-bis (3-amino-4-hydroxyphenyl) adamantane The synthesis was carried out under the same conditions as above. The obtained polyhydroxyamide (hereinafter referred to as polymer III) had a weight average molecular weight of 5700 and a dispersity of 1.3 determined by standard polystyrene conversion.

(Synthesis Example 4)
Synthesis Example 1 except that 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene used in Synthesis Example 1 was replaced with 1,3′-bis (3-amino-4-hydroxyphenyl) adamantane The synthesis was carried out under the same conditions as above. The obtained polyhydroxyamide (hereinafter referred to as polymer IV) had a weight average molecular weight of 7900 and a dispersity of 1.3 determined by standard polystyrene conversion.

(Synthesis Example 5)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to ethylene glycol-bis (4-carboxyphenyl) ether, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2,2 The synthesis was carried out under the same conditions as in Synthesis Example 1 except that it was replaced with '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The obtained polyhydroxyamide (hereinafter referred to as polymer V) had a weight average molecular weight of 10,000 and a dispersity of 1.4 determined by standard polystyrene conversion.

(Synthesis Example 6)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to 1,10-bis (4-carboxyphenoxy) decane and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2, Synthesis was performed under the same conditions as in Synthesis Example 1 except that 2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer VI) had a weight average molecular weight of 11,900 and a dispersity of 1.6, as determined by standard polystyrene conversion.

(Synthesis Example 7)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to 1,3-phenylenediacetic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2,2′-bis ( Synthesis was performed under the same conditions as in Synthesis Example 1 except that 3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer VII) had a weight average molecular weight of 8300 and a dispersity of 1.2 determined by standard polystyrene conversion.

(Synthesis Example 8)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to 1,4-phenylenediacetic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2,2′-bis ( Synthesis was performed under the same conditions as in Synthesis Example 1 except that 3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer VIII) had a weight average molecular weight of 12,300 and a dispersity of 1.4 determined by standard polystyrene conversion.

(Synthesis Example 9)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to 4,4′-diphenyl ether diacetic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2,2′-bis. The synthesis was performed under the same conditions as in Synthesis Example 1 except that (3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer IX) had a weight average molecular weight of 15000 and a dispersity of 1.4 determined by standard polystyrene conversion.

(Synthesis Example 10)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to 1,3-bis (3-carboxyphenoxy) benzene, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2, Synthesis was performed under the same conditions as in Synthesis Example 1 except that 2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer X) had a weight average molecular weight of 17500 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Synthesis Example 11)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to 1,3-bis (carboxypropyl) tetramethyldisiloxane, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2 , 2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was synthesized under the same conditions as in Synthesis Example 1, except that it was replaced with hexafluoropropane. The obtained polyhydroxyamide (hereinafter referred to as polymer XI) had a weight average molecular weight of 12,000 and a dispersity of 1.5 determined by standard polystyrene conversion.

(Synthesis Example 12)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to cyclohexane-1,4-dicarboxylic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2,2′-bis. The synthesis was performed under the same conditions as in Synthesis Example 1 except that (3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer XII) had a weight average molecular weight of 10900 and a dispersity of 1.3 determined by standard polystyrene conversion.

(Synthesis Example 13)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to 1,3-adamantane dicarboxylic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2,2′-bis ( Synthesis was performed under the same conditions as in Synthesis Example 1 except that 3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer XIII) had a weight average molecular weight of 7900 and a dispersity of 1.2 determined by standard polystyrene conversion.

(Synthesis Example 14)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was converted to 1,3-adamantanediacetic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was converted to 2,2′-bis ( Synthesis was performed under the same conditions as in Synthesis Example 1 except that 3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer XIV) had a weight average molecular weight of 6500 and a dispersity of 1.5 determined by standard polystyrene conversion.

(Synthesis Example 15)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was synthesized under the same conditions as in Synthesis Example 1 except for cyclohexane-1,4-dicarboxylic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer XV) had a weight average molecular weight of 10400 and a dispersity of 1.3 determined by standard polystyrene conversion.

(Synthesis Example 16)
The 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was changed to cyclohexane-1,3-dicarboxylic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was changed to 2,2′-bis. The synthesis was performed under the same conditions as in Synthesis Example 1 except that (3-amino-4-hydroxyphenyl) hexafluoropropane was used. The obtained polyhydroxyamide (hereinafter referred to as polymer XVI) had a weight average molecular weight of 19,200 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Synthesis Example 17)
40 mol% of 4,4′-diphenyl ether dicarboxylic acid used in Synthesis Example 1 was added to cyclohexane-1,4-dicarboxylic acid, and 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene was added to 2,2 The synthesis was carried out under the same conditions as in Synthesis Example 1 except that it was replaced with '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The obtained polyhydroxyamide (hereinafter referred to as polymer XVII) had a weight average molecular weight of 30100 and a dispersity of 1.7 determined by standard polystyrene conversion.

(Synthesis Example 18)
Synthesis except that 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene used in Synthesis Example 1 was replaced with 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane The synthesis was performed under the same conditions as in Example 1. The obtained polyhydroxyamide (hereinafter referred to as polymer XVIII) had a weight average molecular weight of 17900 and a dispersity of 1.5 determined by standard polystyrene conversion.

(Synthesis Example 19)
Except for replacing 2,2′-bis (3-amino-4-hydroxyphenyl) isopropylidene used in Synthesis Example 1 with 2,2′-bis (3-amino-4-hydroxyphenyl) sulfone. The synthesis was performed under the same conditions as in Synthesis Example 1. The obtained polyhydroxyamide (hereinafter referred to as polymer XIX) had a weight average molecular weight of 21,600 and a dispersity of 1.6 determined by standard polystyrene conversion.

(Synthesis Example 20)
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 1 was replaced with isophthalic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer XX) had a weight average molecular weight of 13700 and a dispersity of 1.5 determined by standard polystyrene conversion.

(Synthesis Example 21)
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 1 was replaced with 4,4′-biphenyldicarboxylic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer XXI) had a weight average molecular weight of 25,000 and a dispersity of 1.8 determined by standard polystyrene conversion.

Conditions for measuring 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 x2
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 to 11, Reference Examples 1 to 6 and Comparative Examples 1 to 4
A resin obtained by dissolving 10.0 g of the polybenzoxazole precursor obtained in Synthesis Examples 1 to 21 in 15 g of N-methylpyrrolidone was spin-coated on a silicon wafer, dried at 120 ° C. for 3 minutes, and coated with a film thickness of 12 μm. A membrane (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 (200 ° C. cured film (B), 350 ° C. Cured film (C)) was obtained. The infrared absorption spectra of these three types of films were measured, and the absorbance at the peak due to CN stretching vibration near 1540 cm −1 was determined. The dehydration ring closure rate of (B) was calculated from the following formula, assuming that the dehydration ring closure rate of (A) was 0% and the dehydration ring closure rate of (C) was 100%.

測定装置： ＦＴＩＲ‐８３００（株式会社島津製作所製）
上記のようにして得られたポリマーの脱水閉環率を表１に示した。

Measuring device: FTIR-8300 (manufactured by Shimadzu Corporation)
Table 1 shows the dehydration ring closure rate of the polymers obtained as described above.

From the above results, the polymers of Examples 1 to 11 had a higher cyclization rate at 200 ° C. than Comparative Examples 1 to 4.

Examples 12 to 16, Reference Examples 7 to 9 and Comparative Examples 5 and 6
Photosensitive characteristics evaluation The components (b) and (c) and the additive components were blended in the predetermined amounts shown in Table 2 with respect to 100 parts by weight of the polybenzoxazole precursor as the component (a).
The solution was spin-coated on a silicon wafer to form a coating film having a dry film thickness of 3 to 10 μm, and then exposed to i-line (365 nm) using an ultrahigh pressure mercury lamp through an interference filter. 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.

  In Table 2, BLO: γ-butyrolactone, PGMEA: propylene glycol monomethyl ether acetate, NMP: N-methylpyrrolidone, and BLO / NMP indicate that both were used in combination. 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, and D2 are the following compounds.

  Further, the solution 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 3% 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, Tg, elongation, and film properties comparable to those at the time of curing at 320 ° C. were obtained even at 200 ° C. curing . When cured at 200 ° C. in the examples with respect to dehydration ring closure rate was already as high as 70% or more. On the other hand, in the curing at 200 ° C. in the comparative example, the dehydration ring closure rate was 58% or less 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.

Examples 17 to 23 and Reference Example 10
11 parts by weight of B1 is used as the component (b) and 150 parts by weight of N-methylpyrrolidone is used as the component (c) with respect to 100 parts by weight of the polybenzoxazole precursor represented by the polymers X to XII and the polymer XV, and (d) As a component, a thermal acid generator was blended as shown in Table 5, and the dehydration ring closure rate when thermosetting at 200 ° C. and 180 ° C. for 1 hour was measured and calculated in the same manner as in Example 1. The results are also shown in Table 5.

  Thus, by using a thermal acid generator in combination, the dehydration cyclization rate at 200 ° C. is greatly increased as compared with the case of no addition, and a high cyclization rate can be obtained even at a lower temperature.

It is a manufacturing process figure of the semiconductor device of a multilayer wiring structure.

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 (13)

(A) A photosensitive resin composition comprising a polybenzoxazole precursor having a repeating unit represented by formula (I), (b) a photosensitizer, and (c) a solvent.

[In General Formula (I), U or V represents a divalent organic group, and at least one of U or V is any one of groups including structures represented by (UV1) to (UV3) shown below. ]
(UV1): a group containing an alicyclic structure having 6 to 20 carbon atoms , represented by general formula (II), (III), (IV) or (V) ,

(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 h, i, j, k , P, q and r each independently represents an integer of 1 to 6)
(UV2): a group containing a structure represented by the following general formula ,

(Where X is one of the following structures)

(However, n represents an integer of 1 to 6)
(UV3):

Wherein R is independently a hydrogen atom or a monovalent organic group, M is a single bond , —O—, —S—, —SO ₂ — or a divalent organic group, and g and h are each independently an integer of 1 to 4, l including group structures is represented by a 0 or 1)   The photosensitive resin composition according to claim 1, wherein U in the general formula (I) of the component (a) has any one of the following structures.

(However, Z is a C1-C6 hydrocarbon group.)   The photosensitive resin composition according to claim 1 or 2, wherein V in the general formula (I) of the component (a) has any one of the following structures.

(However, Z is a C1-C6 hydrocarbon group.)   The photosensitive resin composition according to claim 1 or 2, wherein V in the general formula (I) of the component (a) has any one of the following structures.

(However, n represents an integer of 1 to 6)   The photosensitive resin composition according to claim 1 or 2, wherein V in the general formula (I) of the component (a) has any one of the following structures.

(However, Z is a C1-C6 hydrocarbon group. Moreover, M is a single bond, -O-, -S-, -SO. ₂ -Or a divalent organic group) Wherein component (b), the photosensitive resin composition according to any one of claims 1 to 5 acid or by light is to generate a radical. Furthermore, the photosensitive resin composition in any one of Claims 1-6 containing the thermal acid generator which generate | occur | produces an acid by heating as (d) component. Polybenzoxazole film according with claim 1-7 photosensitive resin composition according to any one of, is formed by cyclodehydration the polybenzoxazole precursor. A step of coating and drying on a support substrate a photosensitive resin composition according to any one of claims 1 to 7 comprising the steps of exposing the photosensitive resin film obtained by the drying to a predetermined pattern, the exposure A method for producing a pattern, comprising: a step of developing a subsequent photosensitive resin film using an alkaline aqueous solution; and a step of heat-treating the photosensitive resin film after development. 10. The method for producing a pattern according to claim 9 , wherein in the step of heat-treating the photosensitive resin film after development, the heating step irradiates the microwave in pulses while changing the frequency. . The method for producing a pattern according to claim 9 or 10 , wherein, in the step of heat-treating the photosensitive resin film after development, the heat-treatment temperature is 280 ° C or lower. The electronic component which has the layer of the pattern obtained by the manufacturing method of the pattern of Claim 9, 10 or 11 as an interlayer insulation film layer and / or a surface protective film layer. The electronic component according to claim 12 , wherein the electronic component is a magnetoresistive memory (MRAM (Magnetic Resistive Random Access Memory)).

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