JP4793126B2 - Photosensitive resin composition, pattern manufacturing method, and electronic component - Google Patents

Description

  The present invention relates to a photosensitive resin composition excellent in heat resistance containing a polybenzoxazole precursor, a pattern production method using the 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, 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 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. 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 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 polyimide 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 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 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 emerged as a promising next-generation memory, is vulnerable to high-temperature processes, and low-temperature processes are desired. Therefore, even a buffer coat (surface protective film) material can be cured at a low temperature of about 280 ° C. or lower, not at a conventional high temperature of around 350 ° C., and the physical properties of the cured film are cured at a high temperature. Buffer coating materials that can provide incomparable performance have become essential. However, there has been a problem that a buffer coating material that can be cured at such a low temperature and that has performance comparable to that cured at a high temperature has not yet been obtained.

  The present invention has been made to solve the 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 problems, the present invention relates to a photosensitive polybenzoxazole precursor capable of alkali development, and in the general formula (I) or (V) shown below, both or one of U and V is alicyclic. By having a structure, the polybenzoxazole precursor has a high light transmittance, and the dehydration ring closure rate of the resin is high even at about 280 ° C. or lower. It is an object of the present invention to provide a photosensitive resin composition rich in heat resistance that is not different from the physical properties of a cured film.

In addition, since the alicyclic ring structure has a specific configuration, the cured film has a high elongation at break even in a curing process at a lower temperature. In the present invention, by using the photosensitive resin composition, a pattern with a good shape that can be developed with an aqueous alkaline solution, has excellent sensitivity and resolution, and has excellent heat resistance by a low-temperature curing process at 280 ° C. or lower is obtained. A method for manufacturing a pattern 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.

  That is, the photosensitive resin composition according to the present invention contains (a) a polybenzoxazole precursor having a repeating unit represented by the general formula (I), (b) a photosensitizer, and (c) a solvent. It is characterized by.

（式中、Ｕ又はＶは２価の有機基を示し、Ｖは炭素数３〜２０の脂環式環状構造を含む基であり、前記脂環式環状構造に含まれる２つの炭素と、これら２つの炭素にそれぞれ結合される前記ポリベンゾオキサゾール前駆体の主鎖上の元素とで形成される２つの結合における立体配置は、一般式（Ｉ）の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, U or V represents a divalent organic group, V is a group containing an alicyclic ring structure having 3 to 20 carbon atoms, two carbons contained in the alicyclic ring structure, and these The configuration in two bonds formed with the elements on the main chain of the polybenzoxazole precursor bonded to two carbons is 30% or more with respect to the total number of repeating units of the general formula (I). Anti-type.)

In the photosensitive resin composition according to the present invention, V in the general formula (I) of the component (a) is represented by the following general formula (II) or (III): To do.

（式中、Ｒ¹からＲ⁶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の整数を表し、Ｒ¹とＲ¹に隣接する炭素との結合及びＲ⁴とＲ⁴に隣接する炭素との結合における立体配置は、前記一般式（Ｉ）の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, R ¹ to R ⁶ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, a and b each independently represent an integer of 1 to 6 and are adjacent to R ¹ and R ^1. configuration at binding to the carbon adjacent to the binding and R ⁴ and R ⁴ in a, more than 30% are anti-shaped with respect to the total number of repeating units of the general formula (I).)

（式中、Ａは単結合又は２価の有機基を示し、Ｒ⁷からＲ¹⁸は、各々独立に水素又は炭素数１〜６のアルキル基であり、ｃからｆは各々独立に１〜６の整数を表し、Ｒ⁷とＲ⁷に隣接する炭素との結合及びＲ¹⁰とＲ¹⁰に隣接する炭素との結合における立体配置、並びにＲ¹³とＲ¹³に隣接する炭素との結合及びＲ¹⁶とＲ¹⁶に隣接する炭素との結合における立体配置は、それぞれ、前記一般式（Ｉ）の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, A represents a single bond or a divalent organic group, R ⁷ to R ¹⁸ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and c to f are each independently 1 to 6) represents an integer, R ⁷ and the configuration at binding to the carbon adjacent to the binding and R ¹⁰ and R ¹⁰ with the carbon adjacent to R ^7, and binding and R ¹⁶ and the carbon adjacent to R ¹³ and R ¹³ And 30% or more of the steric configuration of the bond between R ¹⁶ and the carbon adjacent to R ¹⁶ is the anti form with respect to the total number of the repeating units of the general formula (I).

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

（式中、Ｕは２価の有機基であり、シクロヘキサン環とシクロヘキサン環に結合する２つのカルボニル基とで形成される２つの結合における立体配置は、一般式（ＩＶ）の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, U is a divalent organic group, and the configuration of two bonds formed by a cyclohexane ring and two carbonyl groups bonded to the cyclohexane ring is the total number of repeating units of the general formula (IV)). On the other hand, 30% or more is anti-type.)

  In the photosensitive resin composition according to the present invention, (a) a copolymer of a polybenzoxazole precursor having an A structural unit and a B structural unit represented by the general formula (V); It comprises (b) a photosensitizer and (c) a solvent.

（式中、Ｕ, Ｖ, Ｗ, Ｘは２価の有機基を示し、Ｕ及びＶの少なくとも一方が炭素数３〜２０の脂環式環状構造を含む基であり、Ｗ及びＸは脂環式環状構造を含まない基であり、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、前記脂環式環状構造に含まれる２つの炭素と、これら２つの炭素にそれぞれ結合される前記ポリベンゾオキサゾール前駆体の主鎖上の元素とで形成される２つの結合における立体配置は、前記Ａ構造単位の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, U, V, W and X represent a divalent organic group, and at least one of U and V is a group containing an alicyclic structure having 3 to 20 carbon atoms, and W and X are alicyclic. Is a group that does not contain a cyclic structure, j and k represent the mole fraction of the A structural unit and the B structural unit, respectively, and the sum of j and k is 100 mol%, and is included in the alicyclic cyclic structure. The configuration at the two bonds formed by two carbons and the elements on the main chain of the polybenzoxazole precursor that are respectively bonded to the two carbons is the total number of repeating units of the A structural unit. 30% or more is anti-type.)

  In the photosensitive resin composition according to the present invention, at least one of U or V in the general formula (V) of the component (a) is represented by the general formula (II) or (III). Features.

（式中、Ｒ¹からＲ⁶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の整数を表し、Ｒ¹とＲ¹に隣接する炭素との結合及びＲ⁴とＲ⁴に隣接する炭素との結合における立体配置は、前記Ａ構造単位の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, R ¹ to R ⁶ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, a and b each independently represent an integer of 1 to 6 and are adjacent to R ¹ and R ^1. configuration at binding to the carbon adjacent to the binding and R ⁴ and R ⁴ in a, more than 30% are anti-shaped with respect to the total number of repeating units of the a structural unit.)

（式中、Ａは単結合又は２価の有機基を示し、Ｒ⁷からＲ¹⁸は、各々独立に水素又は炭素数１〜６のアルキル基であり、ｃからｆは各々独立に１〜６の整数を表し、Ｒ⁷とＲ⁷に隣接する炭素との結合及びＲ¹⁰とＲ¹⁰に隣接する炭素との結合における立体配置、並びにＲ¹³とＲ¹³に隣接する炭素との結合及びＲ¹⁶とＲ¹⁶に隣接する炭素との結合における立体配置は、それぞれ、前記Ａ構造単位の繰り返し単位の総数に対して３０％以上がアンチ形ある。）

(In the formula, A represents a single bond or a divalent organic group, R ⁷ to R ¹⁸ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and c to f are each independently 1 to 6) represents an integer, R ⁷ and the configuration at binding to the carbon adjacent to the binding and R ¹⁰ and R ¹⁰ with the carbon adjacent to R ^7, and binding and R ¹⁶ and the carbon adjacent to R ¹³ and R ¹³ The steric configuration at the bond between R ¹⁶ and the carbon adjacent to R ¹⁶ is 30% or more of the total number of repeating units of the A structural unit.

  In the photosensitive resin composition according to the present invention, the component (a) has an A structural unit and a B structural unit represented by the following general formula (VI). And

（式中、Ｕ,Ｗ,Ｘは２価の有機基を示し、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Ａ構造単位におけるシクロヘキサン環とシクロヘキサン環に結合する２つのカルボニル基とで形成される２つの結合における立体配置は、前記Ａ構造単位の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, U, W and X represent a divalent organic group, j and k represent the mole fraction of the A structural unit and the B structural unit, respectively, and the sum of j and k is 100 mol%, The steric configuration of the two bonds formed by the cyclohexane ring and the two carbonyl groups bonded to the cyclohexane ring in the A structural unit is 30% or more with respect to the total number of repeating units of the A structural unit. )

  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 component (d).

The polybenzoxazole film according to the present invention is formed by using the photosensitive resin composition and dehydrating and ring-closing the polybenzoxazole precursor at a temperature of 280 ° C. or lower .

  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 memory.

  Conventionally, the polybenzoxazole precursor used as the base resin of the photosensitive resin composition is cured at a high temperature of around 350 ° C. in order to dehydrate and ring-close after pattern formation. By using a specific polybenzoxazole photosensitive resin film having a high dehydration ring closure rate even at 280 ° C. or lower as a base resin, performance comparable to that obtained by curing the film at 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.

Further, according to the method for producing a pattern of the present invention, by using the photosensitive resin composition, excellent sensitivity, resolution, adhesiveness, excellent heat resistance even in a low-temperature curing process, low water absorption, good shape Pattern is obtained.
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 contains (a) a polybenzoxazole precursor having a repeating unit represented by the general formula (I), (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.

（式中、Ｕ又はＶは２価の有機基を示し、Ｖは炭素数３〜２０の脂環式環状構造を含む基であり、前記脂環式環状構造に含まれる２つの炭素と、これら２つの炭素にそれぞれ結合される前記ポリベンゾオキサゾール前駆体の主鎖上の元素とで形成される２つの結合における立体配置は、一般式（Ｉ）の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, U or V represents a divalent organic group, V is a group containing an alicyclic ring structure having 3 to 20 carbon atoms, two carbons contained in the alicyclic ring structure, and these The configuration in two bonds formed with the elements on the main chain of the polybenzoxazole precursor bonded to two carbons is 30% or more with respect to the total number of repeating units of the general formula (I). Anti-type.)

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

（式中、Ｕ, Ｖ, Ｗ, Ｘは２価の有機基を示し、Ｕ及びＶの少なくとも一方が炭素数３〜２０の脂環式環状構造を含む基であり、Ｗ及びＸは脂環式環状構造を含まない基であり、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、前記脂環式環状構造に含まれる２つの炭素と、これら２つの炭素にそれぞれ結合される前記ポリベンゾオキサゾール前駆体の主鎖上の元素とで形成される２つの結合における立体配置は、前記Ａ構造単位の繰り返し単位の総数に対して３０％以上がアンチ形である。）
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。

(In the formula, U, V, W and X represent a divalent organic group, and at least one of U and V is a group containing an alicyclic structure having 3 to 20 carbon atoms, and W and X are alicyclic. Is a group that does not contain a cyclic structure, j and k represent the mole fraction of the A structural unit and the B structural unit, respectively, and the sum of j and k is 100 mol%, and is included in the alicyclic cyclic structure. The configuration at the two bonds formed by two carbons and the elements on the main chain of the polybenzoxazole precursor that are respectively bonded to the two carbons is the total number of repeating units of the A structural unit. 30% or more is anti-type.)
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 formulas (I) and (V), the structure of a polyamide that is not a polybenzoxazole precursor, the structure of polybenzoxazole, a polyimide or a polyimide precursor ( The structure of polyamic acid or polyamic acid ester) may be included together with the structure of the polyoxazole precursor of the general formulas (I) and (V).

  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 a hydroxy group represented by the general formulas (I) and (V) is finally subjected to dehydration and ring closure at the time of curing, resulting in heat resistance, mechanical properties, and electrical properties. It is converted into an oxazole form excellent in

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

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

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

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

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

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

  The method for producing the polybenzoxazole precursor in the present invention is not particularly limited. For example, the polybenzoxazole precursor having a repeating unit represented by the general formulas (I) and (V) is generally a dicarboxylic acid derivative and It can be synthesized from hydroxy group-containing diamines. 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, general formulas (I) and (V) will be described in detail.
The polybenzoxazole precursor having a repeating unit represented by the general formula (I) is represented by the following general formula.

（式中、Ｕ又はＶは２価の有機基を示し、Ｖは炭素数３〜２０の脂環式環状構造を含む基であり、前記脂環式環状構造に含まれる２つの炭素と、これら２つの炭素にそれぞれ結合される前記ポリベンゾオキサゾール前駆体の主鎖上の元素とで形成される２つの結合における立体配置は、一般式（Ｉ）の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, U or V represents a divalent organic group, V is a group containing an alicyclic ring structure having 3 to 20 carbon atoms, two carbons contained in the alicyclic ring structure, and these The configuration in two bonds formed with the elements on the main chain of the polybenzoxazole precursor bonded to two carbons is 30% or more with respect to the total number of repeating units of the general formula (I). Anti-type.)

  Here, the “anti form” means that when the alicyclic ring structure forms a part of the main chain of the polybenzoxazole precursor, the two carbons included in the alicyclic ring structure and the two carbons The configuration of two bonds formed with an element (for example, carbon) on the main chain of the polybenzoxazole precursor that is bonded to each of the carbon atoms in the alicyclic ring structure from the carbon included in the alicyclic ring structure is When the direction toward the element is the direction of bonding, it means a state in which the state is directed in the opposite direction.

に示されるように、脂環上の炭素Ｃ₁から一方のポリベンゾオキサゾール前駆体における主鎖上の元素Ｓへの結合の向きに対して、脂環上の炭素Ｃ₄から脂環を構成しない２つの結合の向きのうち炭素Ｃ₄と他方のポリベンゾオキサゾール前駆体における主鎖上の元素Ｔへの結合の向きが、より反対方向を向いている。このような状態が形成されていることをアンチ形と称する。 For example, in the example of a 1,4-substituted cyclohexane ring, the following structural formula (IX)

As shown in FIG. 2, the carbon C ₁ on the alicyclic ring does not constitute the alicyclic ring from the carbon C ₄ on the alicyclic ring, with respect to the bonding direction from the carbon C ₁ on the alicyclic ring to the element S on the main chain in one polybenzoxazole precursor. Of the two bond directions, the bond direction to the element T on the main chain in the carbon C ₄ and the other polybenzoxazole precursor is more in the opposite direction. The formation of such a state is called an anti-type.

In the configuration as described above, it is preferable that 30% or more of the total number of repeating units of the general formula (I) is an anti-form. However, the preferred range varies depending on the structure, and is generally preferably 40% or more, more preferably 50% or more, based on the total number of repeating units of the general formula (I).
Here, the total number of repeating units of the general formula (I) is preferably in the range of about 10 to 1,000. In addition, in order to obtain these desired ratios of the anti-form, for example, it is easily obtained by mixing a compound having a known configuration of the anti-form or the syn-form in a predetermined ratio (for example, mol%).

  Next, a copolymer of a polybenzoxazole precursor having an A structural unit and a B structural unit represented by the general formula (V) used in the present invention is a polybenzoxazole precursor represented by the following formula: Is the body.

（式中、Ｕ, Ｖ, Ｗ, Ｘは２価の有機基を示し、Ｕ及びＶの少なくとも一方が炭素数３〜２０の脂環式環状構造を含む基であり、Ｗ及びＸは脂環式環状構造を含まない基であり、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、前記脂環式環状構造に含まれる２つの炭素と、これら２つの炭素にそれぞれ結合される前記ポリベンゾオキサゾール前駆体の主鎖上の元素とで形成される２つの結合における立体配置は、前記Ａ構造単位の繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, U, V, W and X represent a divalent organic group, and at least one of U and V is a group containing an alicyclic structure having 3 to 20 carbon atoms, and W and X are alicyclic. Is a group that does not contain a cyclic structure, j and k represent the mole fraction of the A structural unit and the B structural unit, respectively, and the sum of j and k is 100 mol%, and is included in the alicyclic cyclic structure. The configuration at the two bonds formed by two carbons and the elements on the main chain of the polybenzoxazole precursor that are respectively bonded to the two carbons is the total number of repeating units of the A structural unit. 30% or more is anti-type.)

Here, the molar fraction of j and k in the formula is such that j = 5 to 85 mol% and k = 15 to 95 mol% in terms of pattern properties, mechanical properties, heat resistance, and chemical resistance. preferable.
In the general formula (V), two bonds formed by two carbons contained in the alicyclic ring structure and elements on the main chain of the polybenzoxazole precursor bonded to the two carbons, respectively. The steric configuration in A is preferably 30% or more in the anti form with respect to the total number of repeating units of the A structural unit, but the preferred range varies depending on the structure, and is generally more preferably 40% or more. Preferably it is 50% or more. Moreover, in order to obtain the ratio of these desired anti-forms, it can be easily obtained by, for example, mixing a compound whose configuration is known to be anti-form or syn-form in a predetermined ratio (for example, mol%).

Next, a preferable group as U will be described.
The group containing an alicyclic structure having 3 to 20 carbon atoms may exist as U or V in the general formulas (I) and (V). As the group containing a skeleton of the alicyclic structure, the alicyclic structure represented by the general formulas (II) and (III) is preferable because the dehydration ring closure rate at 280 ° C. or lower is excellent. The “repeating unit” in the following general formulas (II) and (III) represents a repeating unit of the general formula (I) when U or V is present in the general formula (I), and U or V is When present in the general formula (V), a repeating unit of the A structural unit of the general formula (V) is shown.

（式中、Ｒ¹からＲ⁶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の整数を表し、Ｒ¹とＲ¹に隣接する炭素との結合及びＲ⁴とＲ⁴に隣接する炭素との結合における立体配置は、繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, R ¹ to R ⁶ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, a and b each independently represent an integer of 1 to 6 and are adjacent to R ¹ and R ^1. configuration at binding to the carbon adjacent to the binding and R ⁴ and R ⁴ in a, more than 30% are anti-shaped with respect to the total number of repeating units.)

（式中、Ａは単結合又は２価の有機基を示し、Ｒ⁷からＲ¹⁸は、各々独立に水素又は炭素数１〜６のアルキル基であり、ｃからｆは各々独立に１〜６の整数を表し、Ｒ⁷とＲ⁷に隣接する炭素との結合及びＲ¹⁰とＲ¹⁰に隣接する炭素との結合における立体配置、並びにＲ¹³とＲ¹³に隣接する炭素との結合及びＲ¹⁶とＲ¹⁶に隣接する炭素との結合における立体配置は、繰り返し単位の総数に対して３０％以上がアンチ形である。）

(In the formula, A represents a single bond or a divalent organic group, R ⁷ to R ¹⁸ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and c to f are each independently 1 to 6) represents an integer, R ⁷ and the configuration at binding to the carbon adjacent to the binding and R ¹⁰ and R ¹⁰ with the carbon adjacent to R ^7, and binding and R ¹⁶ and the carbon adjacent to R ¹³ and R ¹³ 30% or more of the steric configuration in the bond between R ¹⁶ and the carbon adjacent to R ¹⁶ is anti-type with respect to the total number of repeating units.

Next, examples of the diamines described above include compounds represented by the following chemical formula (X).

In the chemical formula (X), when the cyclohexane ring has a chair conformation, as shown in the chemical formula (XI) below, the black circle in the formula is a carbon on the aminophenol group, and the bond from C ₁ to the black circle And a bond from C ₂ , C ₃ or C ₄ to a black circle, the anti-form in which the two bond directions are in the most opposite directions, or a mixture of configurational isomers containing 30 mol% or more of the anti-form It is preferable that Thus, when the steric configuration is a trans isomer (anti form) or a mixture of a trans isomer (anti form) and a cis form (syn form) in a certain ratio range, the elongation at break is high even in the curing process at low temperature, More preferred. Among them, the substitution position of the diaminophenol group is preferably 1,4-position. In the case of the 1,4-position, it is consistent with the expressions trans and cis. An example of the representation of this configuration is shown in the following formula (XII).

（式中、Ａは単結合又はＣＨ₂−，−Ｃ（ＣＨ₃）₂−，−Ｏ−，−Ｓ−，−ＳＯ₂−，−ＣＯ−，−（ＣＦ₃）₂−、−ＮＨＣＯ−である。） Other examples of diamines include compounds represented by the following general formula (XIII).

(In the formula, A is a single bond or CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, — (CF ₃ ) ₂ —, —NHCO—). .)

  In addition, as shown in Formula (XIV), the configuration of two alicyclic ring structures adjacent to A in General Formula (XIII) is a configurational isomer containing an anti form or an anti form with respect to A, respectively. A mixture is preferable, and the substitution position of the diaminophenol group is 4,4′-position, which is more preferable because the elongation at break is high even in the curing process at low temperature. An example of such a configuration is shown in the following formula (XV).

  In addition, as U or W diamines, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (3-amino-4-hydroxy) Phenyl) 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 and other aromatic diamines other than those mentioned above, but are not limited thereto. Is not to be done. These diamines can be used alone or in combination of two or more.

  In addition, when using diamine which has these alicyclic structures, it is also possible to use together the diamine shown to the said Chemical formula (IX) and General formula (XI) 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 formulas (I) and (V) is generally a dicarboxylic acid residue that reacts with a diamine to form a polyamide structure.
In the present invention, as V, the group containing an alicyclic structure having 3 to 20 carbon atoms may exist as V or V in the general formulas (I) and (V). As the group containing an alicyclic structure skeleton, the structure represented by the general formulas (II) and (III) has high heat resistance, high transparency in the ultraviolet and visible light range, and below 280 ° C. Excellent in terms of high dehydration ring closure rate.

  Examples of the alicyclic structure represented by the general formula (II) or (III) as such a dicarboxylic acid include compounds represented by the following chemical formula (XVI).

  In the formula (XVI), as shown in the following formula (XVII), an anti form in which two bonds from a carbon to a black circle on the alicyclic ring are in the opposite directions, with the black circle in the formula as a carboxyl group, or the anti form Is preferably a configurational isomer mixture containing 30 mol% or more. Of these, the substitution position of the dicarboxylic acid is 1,3-position for the cyclobutane ring and 1,4-position for the cyclohexane ring, and the steric configuration is the trans isomer (anti form) or the trans isomer (anti form) and the cis form ( It is more preferable that it is a mixture with a thin form) because it has not only high light transmittance but also high elongation at break even in a low temperature curing process. An example of the configuration of such a trans isomer and cis isomer is shown in the following formula (XVIII).

（式中、Ａは単結合又はＣＨ₂−，−Ｃ（ＣＨ₃）₂−，−Ｏ−，−Ｓ−，−ＳＯ₂−，−ＣＯ−，−（ＣＦ₃）₂−、−ＮＨＣＯ−である。） Other examples of dicarboxylic acids include compounds represented by general formula (XIX).

(In the formula, A is a single bond or CH ₂ —, —C (CH ₃ ) ₂ —, —O—, —S—, —SO ₂ —, —CO—, — (CF ₃ ) ₂ —, —NHCO—). .)

  As shown in the formula (XIV), the configuration of two alicyclic ring structures adjacent to A is preferably an anti-form or a mixture of configuration isomers including an anti-form with respect to A, It is more preferable that the substitution position of the dicarboxyl group is 4,4′-position because not only is the light transmittance high, but also the elongation at break is high in the curing process at low temperature. Examples of such a configuration of the alicyclic skeleton are the same as those in the formula (XV).

  Other V, X or Z 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 -Aromatic dicarboxylic acids such as butylisophthalic acid, 5-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 precursors represented by the general formulas (VII) and (VIII), the divalent organic group represented by Y generally reacts with a dicarboxylic acid to form a polyamide structure. It is a residue derived from diamine (however, other than dihydroxydiamine forming 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 structures of U, V, X, and Y in the general formulas (I) and (V), a radical may be used as the component (b). By using what is generated, that is, a photopolymerization initiator, 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.

((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) 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 in combination with a specific resin having a high dehydration ring closure rate of about 280 ° C. or less of the present invention, the physical properties of the film after curing can be achieved even at low temperature curing. Performance comparable to that cured at high temperature.

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

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

Further, as the component (d), as shown in the following chemical formula (XX), 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. Examples of R ¹ include a cyano group, and examples of R ² include a methoxyphenyl group and a phenyl group.

In addition, as the component (d), as shown in the following chemical formula (XXI), 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. 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, a compound with a molecular weight of 1,500 or less is generally preferable. For example, those represented by the following general formula (XXII) are particularly preferred 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.

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

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

  The 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 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.

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

  Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, 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.

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

  Examples of such surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like, 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).

[Pattern manufacturing method]
Next, a pattern manufacturing method according to the present invention will be described. The pattern production method of the present invention includes a step of applying the above-described photosensitive resin composition onto a support substrate and drying, a step of exposing the photosensitive resin film obtained by the drying step to a predetermined pattern, and after the exposure. A polybenzoxazole pattern can be obtained through a step of developing the photosensitive resin film and a step of heat-treating the photosensitive resin film after the development. 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 photosensitive resin composition is applied on a support substrate such as a glass substrate, a semiconductor, a metal oxide insulator (eg, TiO ₂ , SiO _2, etc.) or silicon nitride. After spin-coating the conductive resin composition using a spinner or the like, it is dried using a hot plate, 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 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 Nos. 2587148 and 3031434, dehydration and ring closure of a polyimide precursor using microwaves are studied. In US Pat. No. 5,739,915, when a polyimide precursor thin film is dehydrated and closed using microwaves, there is a method for avoiding damage to the polyimide thin film or the base material by irradiating with the frequency changed in a short period. Proposed.

  When microwaves are irradiated in pulses while changing the frequency, standing waves can be prevented and the substrate surface can be heated uniformly. 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 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.

  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.

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

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

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

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

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

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

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

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

  Next, the surface protective film 8 is formed. In the example of FIGS. 1-5, this surface protective film is formed as follows. That is, the photosensitive resin composition 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 (Magnetic 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 polybenzoxazole precursor In a 0.5 liter flask equipped with a stirrer and a thermometer, 15.50 g of 1,4-transcyclohexanedicarboxylic acid (anti-form 100 mol%), N-methyl After charging 110 g of pyrrolidone and cooling the flask to 5 ° C., 21.41 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 1,4-transdicarboxylic acid chloride. Next, in a 0.5 liter flask equipped with a stirrer and a thermometer, 110 g of N-methylpyrrolidone was charged, and 29.67 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added. After stirring and dissolving, 14.24 g of pyridine was added, and while maintaining the temperature at 0 to 5 ° C., a solution of 1,4-transdicarboxylic acid chloride was added dropwise over 30 minutes, and then stirring was continued for 30 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 weight average molecular weight calculated | required by GPC method standard polystyrene conversion of the polymer I was 51,000, and dispersion degree was 1.8.

(Synthesis Example 2)
The 1,4-transcyclohexanedicarboxylic acid used in Synthesis Example 1 was replaced with 1,4-cyclohexanedicarboxylic acid in a 1: 1 mixture of cis and trans isomers (50 mol% syn form: 50 mol% anti form). Except for the above, synthesis was performed under the same conditions as in Synthesis Example 1. The obtained polyhydroxyamide (hereinafter referred to as polymer II) had a weight average molecular weight of 36,300 and a dispersity of 1.8 determined by standard polystyrene conversion.

(Synthesis Example 3)
The same conditions as in Synthesis Example 1 except that 42 mol% of 1,4-cyclohexanedicarboxylic acid in the 1: 1 mixture of cis and trans isomers used in Synthesis Example 2 was replaced with 4,4′-diphenyl ether dicarboxylic acid. Was synthesized. The obtained polyhydroxyamide (hereinafter referred to as polymer III) had a weight average molecular weight of 34,200 and a dispersity of 2.1 determined by standard polystyrene conversion.

(Synthesis Example 4)
Synthesis was performed under the same conditions as in Synthesis Example 1 except that 42 mol% of 1,4-transcyclohexanedicarboxylic acid used in Synthesis Example 1 was replaced with 4,4′-diphenyl ether dicarboxylic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer IV) had a weight average molecular weight of 41,600 and a dispersity of 2.4 determined by standard polystyrene conversion.

(Synthesis Example 5)
The conditions were the same as in Synthesis Example 1 except that 1,4-transcyclohexanedicarboxylic acid used in Synthesis Example 1 was replaced with hexafluoropropyl-4,4′-dicyclohexylpropyldicarboxylic acid, which is a mixture of configurational isomers. Were synthesized. The obtained polyhydroxyamide (hereinafter referred to as polymer V) had a weight average molecular weight of 28,400 and a dispersity of 1.9, as determined by standard polystyrene conversion.

(Synthesis Example 6)
The synthesis was performed under the same conditions as in Synthesis Example 1 except that 1,4-transcyclohexanedicarboxylic acid used in Synthesis Example 1 was replaced with 4,4′-diphenyl ether dicarboxylic acid. The obtained polyhydroxyamide (hereinafter referred to as polymer VI) had a weight average molecular weight of 17,900 and a dispersity of 1.5 determined by standard polystyrene conversion.

(Synthesis Example 7)
Except for replacing 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane used in Synthesis Example 1 with 2,2′-bis (3-amino-4-hydroxyphenyl) sulfone Was synthesized 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 performed under the same conditions as in Synthesis Example 1 except that 1,4-transcyclohexanedicarboxylic acid used in Synthesis Example 1 was replaced with 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.

(Synthesis Example 9)
1,4-transcyclohexanedicarboxylic acid used in Synthesis Example 1 was converted to 1,4-cyclohexanedicarboxylic acid in a mixture of a commercially available cis isomer and trans isomer 3: 1 (syn form 75 mol%: anti form 25 mol%). The synthesis was performed under the same conditions as in Synthesis Example 1 except that The obtained polyhydroxyamide (hereinafter referred to as polymer VIV) had a weight average molecular weight of 38,900 and a dispersity of 1.7 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 1-4
A resin solution obtained by dissolving 10.0 g of the polybenzoxazole precursor obtained in Synthesis Examples 1 to 9 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%.

  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 50%, and 20% to 26% of the aromatic polybenzoxazole in Comparative Examples 1 to 3 It was higher than

Examples 6 to 10 and Comparative Examples 4 to 6
(Photosensitive characteristic evaluation)
With respect to 100 parts by weight of the polybenzoxazole precursor as the component (a), the components (b) and (c) and other additive components are blended in the predetermined amounts shown in Table 2, and the photosensitive resin composition A solution was obtained.

  In 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, and D2 are compounds represented by the following chemical formulas (XXIII) and (XXIV), respectively.

  The obtained photosensitive resin composition 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 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 3.

As described above, the photosensitive resin composition of the present invention obtained film properties comparable to those when cured at 320 ° C. even when cured at 200 ° C., as shown in Table 4, for Tg and elongation. .
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 70% or more. Further, the elongation at break at 200 ° C. was 10% or higher, which was higher than that of the comparative example. Examples 6 and 7 having a large amount of trans cyclohexane skeleton in the polybenzoxazole skeleton had higher elongation at break than Comparative Example 4. 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 heat resistance even when used in a low-temperature curing process, and a pattern having a good shape can be obtained. Therefore, electronic components, particularly MRAM that requires low-temperature curing, etc. Suitable for manufacturing.

  Next, a thermal acid generator as a component (d) was further blended in the solutions prepared in Examples 6 to 10 as shown in Table 4. In Table 4, the compounds represented by the following chemical formula (XXV) 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 4.

  As is apparent from Table 4, 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 specific polybenzoxazole photosensitive resin film having a high dehydration ring closure rate even at a low temperature as a base resin, so that the physical properties of the cured film are cured at a high temperature. Performance comparable to that obtained. Further, according to the method for producing a pattern of the present invention, by using the photosensitive resin composition, excellent sensitivity, resolution, adhesiveness, excellent heat resistance even in a low-temperature curing process, low water absorption, good shape Pattern is obtained. 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 (15)

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. .

(In the formula, U or V represents a divalent organic group, V is a group containing an alicyclic ring structure having 3 to 20 carbon atoms, two carbons contained in the alicyclic ring structure, and these The configuration in two bonds formed with the elements on the main chain of the polybenzoxazole precursor bonded to two carbons is 30% or more with respect to the total number of repeating units of the general formula (I). Anti-type.) V in general formula (I) of said (a) component is represented by the following general formula (II) or (III), The photosensitive resin composition of Claim 1 characterized by the above-mentioned.

(In the formula, R ¹ to R ⁶ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, a and b each independently represent an integer of 1 to 6 and are adjacent to R ¹ and R ^1. configuration at binding to the carbon adjacent to the binding and R ⁴ and R ⁴ in a, more than 30% are anti-shaped with respect to the total number of repeating units of the general formula (I).)

(In the formula, A represents a single bond or a divalent organic group, R ⁷ to R ¹⁸ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and c to f are each independently 1 to 6) represents an integer, R ⁷ and the configuration at binding to the carbon adjacent to the binding and R ¹⁰ and R ¹⁰ with the carbon adjacent to R ^7, and binding and R ¹⁶ and the carbon adjacent to R ¹³ and R ¹³ And 30% or more of the steric configuration of the bond between R ¹⁶ and the carbon adjacent to R ¹⁶ is the anti form with respect to the total number of the repeating units of the general formula (I). The said (a) component is represented by the general formula (IV) shown below, The photosensitive resin composition of Claim 1 characterized by the above-mentioned.

(In the formula, U is a divalent organic group, and the configuration of two bonds formed by a cyclohexane ring and two carbonyl groups bonded to the cyclohexane ring is the total number of repeating units of the general formula (IV)). On the other hand, 30% or more is anti-type.) (A) a copolymer of a polybenzoxazole precursor having the A structural unit and the B structural unit represented by the general formula (V), (b) a photosensitizer, and (c) a solvent. The photosensitive resin composition characterized by the above-mentioned.

(In the formula, U, V, W and X represent a divalent organic group, and at least one of U and V is a group containing an alicyclic structure having 3 to 20 carbon atoms, and W and X are alicyclic. Is a group that does not contain a cyclic structure, j and k represent the mole fraction of the A structural unit and the B structural unit, respectively, and the sum of j and k is 100 mol%, and is included in the alicyclic cyclic structure. The configuration at the two bonds formed by two carbons and the elements on the main chain of the polybenzoxazole precursor that are respectively bonded to the two carbons is the total number of repeating units of the A structural unit. 30% or more is anti-type.) The photosensitive resin composition according to claim 4, wherein at least one of U or V in the general formula (V) of the component (a) is represented by the general formula (II) or (III).

(In the formula, R ¹ to R ⁶ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, a and b each independently represent an integer of 1 to 6 and are adjacent to R ¹ and R ^1. configuration at binding to the carbon adjacent to the binding and R ⁴ and R ⁴ in a, more than 30% are anti-shaped with respect to the total number of repeating units of the a structural unit.)

(In the formula, A represents a single bond or a divalent organic group, R ⁷ to R ¹⁸ are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and c to f are each independently 1 to 6) represents an integer, R ⁷ and the configuration at binding to the carbon adjacent to the binding and R ¹⁰ and R ¹⁰ with the carbon adjacent to R ^7, and binding and R ¹⁶ and the carbon adjacent to R ¹³ and R ¹³ The steric configuration at the bond between R ¹⁶ and the carbon adjacent to R ¹⁶ is 30% or more of the total number of repeating units of the A structural unit. The photosensitive resin composition according to claim 5, wherein the component (a) has an A structural unit and a B structural unit represented by the following general formula (VI).

(In the formula, U, W and X represent a divalent organic group, j and k represent the mole fraction of the A structural unit and the B structural unit, respectively, and the sum of j and k is 100 mol%, The steric configuration of the two bonds formed by the cyclohexane ring and the two carbonyl groups bonded to the cyclohexane ring in the A structural unit is 30% or more with respect to the total number of repeating units of the A structural unit. )   The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (b) is a photosensitive agent that generates an acid or a radical by light.   Furthermore, the thermal resin generator which generate | occur | produces an acid by heating is included as (d) component, The photosensitive resin composition of any one of Claims 1-7 characterized by the above-mentioned. 9. The photosensitivity according to claim 8, wherein the thermal acid generator (d) is a compound that generates any one of arylsulfonic acid, perfluoroalkylsulfonic acid, and alkylsulfonic acid by heating. Resin composition. It is formed by using the photosensitive resin composition according to any one of claims 1 to 9 and dehydrating and ring-closing the polybenzoxazole precursor at a temperature of 280 ° C or lower. Polybenzoxazole film. Among of claims 1 9, comprising the steps of coating and drying on a support substrate a photosensitive resin composition described in any one, exposing the photosensitive resin film obtained by the 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. The pattern manufacturing method according to claim 11 , 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 11 or 12 , wherein the heat treatment temperature is 280 ° C or lower in the step of heat-treating the photosensitive resin film after development. An electronic component comprising a layer of a pattern obtained by the method for producing a pattern according to any one of claims 11 to 13 , as an interlayer insulating film layer and / or a surface protective film layer. The electronic component according to claim 14 , wherein the electronic component is a magnetoresistive memory.

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