JP2008015060A - Photosensitive polyamide acid ester composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive polyamide acid ester composition useful to manufacture electrical/electronic materials and excellent in stability in room temperature over a long term. <P>SOLUTION: This photosensitive polyamide acid ester composition has (A) 100 points of mass of polyamide acid ester having repeated units as expressed in general Formula (1), wherein R contains unsaturated carbon-carbon bonding, (B) 1-15 mass parts of photoinitiator, and (C) 30-600 mass parts of solvent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive polyamic acid ester composition having excellent room temperature storage stability over time.

Polyimide resin is attracting attention as a material related to microelectronics because of its high thermal and chemical stability, low dielectric constant, and excellent planarization ability, and is used as a semiconductor surface protective film or interlayer insulating film, or Widely used as a material for multi-chip modules.
In the case of manufacturing a semiconductor device using a polyimide resin, a polyimide resin film is usually formed on a substrate and a desired pattern is formed using a lithography technique. Specifically, an indirect pattern forming method is used in which a photoresist pattern is formed on a polyimide resin film using a photoresist and a photomask, and then polyimide resin is patterned by etching. However, in this method, first, a photoresist pattern to be a mask is formed on the polyimide resin film, then the polyimide resin is etched, and finally the unnecessary photoresist pattern is peeled off. Therefore, the process is complicated, and the resolution is low because of indirect pattern formation. Further, since it is necessary to use a toxic substance such as hydrazine as a solvent for etching, there is a safety problem.

In order to overcome the above problems, a method of introducing a photopolymerizable photosensitive group into a polyimide precursor and directly forming a pattern on the polyimide precursor film has been put into practical use. For example, a film made of a polyimide precursor formed by bonding a compound having a double bond to a polyamic acid derivative via an ester bond, an amide bond, or an ionic bond, and a photosensitive polyimide precursor composition containing a photoinitiator or the like. Forming a pattern using means for insolubilizing the polyimide precursor of the exposed portion of the coating film by exposing it through a photomask having a pattern, and subjecting it to a development treatment. A method of converting a polyimide precursor to a polyimide having thermal stability by removing the photosensitive group component by heating has been proposed.
This technology is generally called photosensitive polyimide technology. This technique overcomes the problems associated with processes using the conventional non-photosensitive polyimide precursor described above. Therefore, the polyimide pattern is often formed by the above-described photosensitive polyimide technology.
In addition, a part of the polyimide precursor is a carboxyl group. By using a photosensitive group having a secondary carbon as a bonding point in the compound having the above double bond, high-resolution development with an alkaline aqueous solution is possible with high sensitivity. A photosensitive polyimide precursor composition is provided (see Patent Document 1).

In recent years, there has been a demand for improvement in resolution when forming a pattern of a polyimide film used in a semiconductor device or the like. In the process using the non-photosensitive polyimide before the development of the above-mentioned photosensitive polyimide technology, high resolution could not be obtained. The integration rate and accuracy were limited. On the other hand, when the photosensitive polyimide technology is used, a high resolution can be obtained at the time of pattern formation, so that a semiconductor device with a high integration rate and high accuracy can be manufactured. This will be described below.
For example, when manufacturing a memory element or the like, in order to increase the yield of a product, an operation of making a spare circuit in advance and cutting unnecessary circuits after the product is inspected is performed. In the process using conventional non-photosensitive polyimide, unnecessary circuit cutting was performed before the formation of the polyimide pattern, whereas in the process using photosensitive polyimide, the resolution at the time of polyimide pattern formation is high, A hole for cutting an unnecessary circuit in the pattern is provided, and the preliminary circuit can be cut after the polyimide pattern is formed. Therefore, it becomes possible to cut the spare circuit at a stage closer to the completion time of the final product, and a higher product yield is achieved.

By the way, a semiconductor device (hereinafter also referred to as “element”) is mounted on a printed circuit board by various methods in accordance with purposes. A common element is a wire bonding method in which a thin wire is connected from an external terminal (pad) of the element to a lead frame. However, as the speed of the element has increased and the operating frequency has reached GHz, in today's packaging, The difference in the wiring length between the terminals has led to the influence of the device operation. For this reason, when mounting elements for high-end applications, it is necessary to accurately control the length of the mounting wiring, and wire bonding makes it impossible to meet the requirements.
Accordingly, flip chip mounting has been proposed in which a rewiring layer is formed on the surface of a semiconductor chip, bumps (electrodes) are formed thereon, the chip is flipped over, and mounted directly on a printed circuit board. Flip chip mounting is used for high-end devices that handle high-speed signals because the wiring distance can be accurately controlled, and because of the small mounting size, the demand is rapidly expanding. When polyimide is used for flip chip mounting, the polyimide is required to have resistance to a resist stripping solution at high temperatures and heat resistance that can withstand solder reflow. Therefore, in addition to the excellent pattern formability and heat resistance as described above, the photosensitive polyimide resin for the material of the rewiring layer has performance such as chemical resistance to the resist stripping solution used in the process. It is important.

  Also, in recent years, the mounting method of a semiconductor device on a printed wiring board has been changed from a conventional mounting method using metal pins and tin-lead eutectic solder to a polyimide resin coating such as CSP (chip size packaging) that can be mounted at higher density. Is changing to a structure that directly contacts solder bumps. That is, the polyimide resin coating film comes into contact with the flux in a solder bump reflow process and the like, and further heat resistance has been required. Further, in the semiconductor device manufacturing process, from the viewpoint of high efficiency and low cost, there is a significant movement to increase the diameter of a silicon wafer as a substrate to 300 mm. In the process in which the photosensitive polyimide resin precursor composition is applied onto a silicon wafer and converted into a polyimide resin coating film by heating, warpage occurs in the silicon wafer due to residual stress. That is, the situation where a polyimide resin coating film is used for a large-diameter silicon wafer has arisen, and a further reduction in residual stress has been demanded.

Therefore, the heat resistance is improved by a polyamide obtained by copolycondensation of a phthalic acid compound having a specific functional group with a tetracarboxylic acid compound, and a part of the diamine unit of the polyamide is a diamine unit having a siloxane bond. It has been proposed to reduce the residual stress of the coated film after curing (see Patent Document 2).
In order to cope with such various processes, it is necessary to combine with various kinds of initiators, sensitizers and the like. However, depending on the composition corresponding to the special process, the acidity and basicity in the varnish system becomes higher than the conventional composition, and the stability of the photosensitive polyamic acid ester composition is greatly lowered. However, the solution has not yet been proposed, and it is dealt with by setting a short shelf life guarantee period for the storage stability of the photosensitive polyamic acid ester composition. Therefore, development of a photosensitive polyamic acid ester composition excellent in storage stability with time regardless of the composition is strongly desired.

JP 2000-206692 A WO 06/008991 pamphlet

  An object of the present invention is to provide a photosensitive polyamic acid ester composition excellent in stability over time even under standing conditions at room temperature, a method for forming a polyimide pattern using the photosensitive composition, and a semiconductor device having the polyimide pattern. And

  This inventor earnestly examined in order to develop the photosensitive polyamic-acid ester composition which can be used in order to form the polyimide pattern which has the target outstanding characteristic. As a result, it was found that when used as a raw material for the polyamic acid ester, those having a photosensitive group having a secondary carbon as a bonding point show high room temperature aging stability regardless of the composition. The present invention has been made based on these new findings.

〔式中、Ｘは４価の有機基、Ｘ’は下記式（２）で表される基から選ばれる２価の有機基を示す。ＹおよびＹ’は２価の有機基、Ｒは下記式（３）で示される構造の二級炭素を結合点として持つ１価の感光性基を示す。また、ｍは正の整数、ｎは０または正の整数であって、０．５≦ｍ／（ｍ＋ｎ）≦１．０である。

（式中、Ｒ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、Ｒ₆ は１価の有機基であり、Ｒ₅ は２価の有機基である。なお、式（２）中の芳香族環上の水素原子は、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、フッ素原子、及びトリフルオロメチル基からなる群の中から選ばれる少なくとも１種の基で置換されていても良い。）

（Ａは化学線により重合可能な炭素−炭素二重結合を含む１価の有機基を示し、Ｂは１価の有機基を示す。）〕 That is, the first of the present invention is (A) 100 parts by mass of a polyamic acid ester composed of a repeating unit represented by the following general formula (1), (B) 1 to 15 parts by mass of a photoinitiator, and (C) a solvent. It is a photosensitive polyamic-acid ester composition characterized by including 30-600 mass parts.

[Wherein, X represents a tetravalent organic group, and X ′ represents a divalent organic group selected from the group represented by the following formula (2). Y and Y ′ represent a divalent organic group, and R represents a monovalent photosensitive group having a secondary carbon having a structure represented by the following formula (3) as a bonding point. M is a positive integer, n is 0 or a positive integer, and 0.5 ≦ m / (m + n) ≦ 1.0.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₆ are monovalent organic groups, and R ₅ is a divalent organic group. In addition, on the aromatic ring in formula (2) The hydrogen atom is at least one group selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a fluorine atom, and a trifluoromethyl group. It may be replaced.)

(A represents a monovalent organic group containing a carbon-carbon double bond polymerizable by actinic radiation, and B represents a monovalent organic group.)]

In the second aspect of the present invention, (1) the first photosensitive polyamic acid ester composition of the present invention is formed on a substrate in the form of a layer or a film, and (2) exposed with actinic radiation through a mask, A method for producing a cured relief pattern, which comprises directly irradiating a light beam, an electron beam or an ion beam, (3) eluting or removing an exposed portion or irradiated portion, and (4) heat-treating the obtained relief pattern. is there.
A third aspect of the present invention is a semiconductor device having a polyimide pattern formed by the second manufacturing method of the present invention.

  According to the present invention, it was possible to provide a polyamic acid ester composition having excellent room temperature stability regardless of the composition, a method for forming a polyimide pattern using the photosensitive composition, and a semiconductor device having the polyimide pattern.

〔式中、Ｘは４価の有機基、Ｘ’は下記式（２）で表される基から選ばれる２価の有機基を示す。ＹおよびＹ’は２価の有機基、Ｒは下記式（３）で示される構造の二級炭素を結合点として持つ１価の感光性基を示す。また、ｍは正の整数、ｎは０または正の整数であって、０．５≦ｍ／（ｍ＋ｎ）≦１．０である。

（式中、Ｒ₁ 、Ｒ₂ 、Ｒ₃ 、Ｒ₄ 、Ｒ₆ は１価の有機基であり、Ｒ₅ は２価の有機基である。なお、式（２）中の芳香族環上の水素原子は、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ−ブチル基、フッ素原子、及びトリフルオロメチル基からなる群の中から選ばれる少なくとも１種の基で置換されていても良い。）

（Ａは化学線により重合可能な炭素−炭素二重結合を含む１価の有機基を示し、Ｂは１価の有機基を示す。）〕 Hereinafter, embodiments of the present invention will be described in detail.
<Photosensitive polyamic acid ester composition>
(A) Polyamic acid ester The polyamic acid ester which is a component of the composition of the present invention is a polyamic acid ester composed of a repeating unit represented by the following general formula (1), and is composed of an acid dianhydride or dicarboxylic acid and a diamine. It can be obtained by a condensation reaction.

[Wherein, X represents a tetravalent organic group, and X ′ represents a divalent organic group selected from the group represented by the following formula (2). Y and Y ′ represent a divalent organic group, and R represents a monovalent photosensitive group having a secondary carbon having a structure represented by the following formula (3) as a bonding point. M is a positive integer, n is 0 or a positive integer, and 0.5 ≦ m / (m + n) ≦ 1.0.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₆ are monovalent organic groups, and R ₅ is a divalent organic group. In addition, on the aromatic ring in formula (2) The hydrogen atom is at least one group selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a fluorine atom, and a trifluoromethyl group. It may be replaced.)

(A represents a monovalent organic group containing a carbon-carbon double bond polymerizable by actinic radiation, and B represents a monovalent organic group.)]

  The X group in the general formula (1) is composed of a compound having a tetravalent organic group, and usually an aromatic tetracarboxylic acid or a derivative thereof is mainly used. Examples of such compounds include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic acid Dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic Acid dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5 6-tetracarboxylic dianhydride 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5 8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8 -Tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic acid Anhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyltetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -p -Terphenyl tetracarboxylic dianhydride, 2,3,3 ", 4" -p Terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4- Dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-di Carboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene 3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene -1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, Cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride Thiophene-2,3,4,5-tetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and the like. Limited to these Not shall. Moreover, in using these, it may be individual or a mixture of 2 or more types.

In the polyamic acid ester, the dicarboxylic acid X ′ (COOH) ₂ having a divalent organic group represented by the formula (1) in the repeating unit is specifically a 5-aminoisophthalic acid derivative. is there. Derivatives can be divided into the following three systems.
The derivative of system 1 reacts with the amino group of 5-aminoisophthalic acid and an acid chloride, acid anhydride, isocyanate, or epoxy compound having a thermal cross-linking group. It is a compound into which a crosslinking group has been introduced.
As the thermal crosslinking group, those that cause a self-crosslinking reaction in the range of 150 to 400 ° C. are desirable. Norbornene group, glycidyl group, cyclohexene group, ethynyl group, allyl group, aldehyde group, benzocyclobutene group, furyl group, furfuryl Preferred examples include a group, dimethoxydimethylamino group, dihydroxydimethylamino group, alkynyl group, alkenyl group, oxetane group, methacrylate group, acrylate group, cyano group and thiophene group.

  Specific examples of the acid chloride, acid anhydride, isocyanate, or epoxy compound having a thermal crosslinking group include 5-norbornene-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2. , 3,6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic anhydride, 4-ethynyl-1,2-phthalic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride 1-cyclohexene-1,2-dicarboxylic anhydride, maleic anhydride, 3-cyclohexene-1-carboxylic acid chloride, anhydrous endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-furancarboxylic acid chloride, Crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propionic acid chloride, tetrolic acid chloride, citraconic anhydride, itaconic anhydride, thiophene 2-acetyl chloride, isocyanate ethyl methacrylate, allyl succinic anhydride, glycidyl Examples include methacrylate and allyl glycidyl ether.

The derivative of System 2 is a compound in which the amino group of 5-aminoisophthalic acid is protected with a urethane-type protecting group, an acyl-type protecting group, an alkyl-type protecting group, a silicon-type protecting group, a urea-type protecting group, or the like. This protecting group is selected so that the polybenzoxazole precursor is eliminated in the step of ring closure by heating, and the amino group is regenerated. The regenerated amino group causes a cross-linking reaction with a part of the polymer main chain or the terminal part.
Examples of urethane-type protecting groups include benzyloxycarbonyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isobutyloxycarbonyl group, t-butyloxycarbonyl group, p-nitrobenzyloxycarbonyl group, p-methoxy. Examples include a benzyloxycarbonyl group, an isobornylbenzyloxycarbonyl group, and a p-biphenylisopropylbenzyloxycarbonyl group.

  In order to protect the amino group of 5-aminoisophthalic acid with a urethane-type protecting group, the following compounds are specifically used. Chlorocarbonic acid methyl ester, chlorocarbonic acid ethyl ester, chlorocarbonic acid n-propyl ester, chlorocarbonic acid isopropyl ester, chlorocarbonic acid isobutyl ester, chlorocarbonic acid 2-ethoxy ester, chlorocarbonic acid-s-butyl ester, chlorocarbonic acid benzyl ester, chlorocarbonic acid 2 Ethyl hexyl ester, chlorocarbonic acid allyl ester, chlorocarbonic acid phenyl ester, chlorocarbonic acid 2,2,2-trichloroethyl ester, chlorocarbonic acid-2-butoxyethyl ester, chlorocarbonic acid-p-nitrobenzyl ester, chlorocarbonic acid-p-methoxy Chloro carbonates such as benzyl ester, chlorocarbonic acid isobornyl benzyl ester, chlorocarbonic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino 2-phenylacetonitrile, S-t-butyloxycarbonyl-4,6-dimethyl - thiopyrimidine, di -t- butyl - dicarbonate and the like.

Acyl-type protecting groups include formyl, phthaloyl, dithiasuccinoyl, tosyl, mesyl, o-nitrophenylsulfenyl, o-nitropyridinesulfenyl, and diphenylphosphinyl. . Examples of the acyl-type protecting reagent include N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride and the like.
Examples of the alkyl-type protecting group include a triphenylmethyl group and a 2-benzoyl-1-methylvinyl group. Examples of the alkyl type protecting reagent include trityl chloride.
Examples of the silicon-type protecting group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, and t-butyldiphenylsilyl group. Silicon type protective reagents include trimethylchlorosilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane , Trimethylsilyldiphenylurea, bis (trimethylsilyl) urea and the like.

As the urea-type protecting group, 5-aminoisophthalic acid and various monoisocyanate compounds may be reacted. Examples of the monoisocyanate compound include isocyanic acid phenyl ester, isocyanic acid n-butyl ester, isocyanic acid n-octadecyl ester, and isocyanic acid o-tolyl ester. Examples of the monoisocyanate compound include phenyl isocyanate, n-butyl isocyanate, n-octadecyl isocyanate, and o-tolyl isocyanate.
The derivative of system 3 is a compound obtained by reacting the amino group of 5-aminoisophthalic acid with a dicarboxylic anhydride.

  Y and Y 'in the general formula (1) are divalent organic groups, and aromatic diamines and / or derivatives thereof are usually used. Examples of such a compound include m-phenylenediamine, 1-isopropyl-2,4-phenylenediamine, p-phenylenediamine, 4,4′-diamino-diphenylpropane, 3,3′-diamino-diphenylpropane, 4,4′-diamino-diphenylethane, 3,3′-diamino-diphenylethane, 4,4′-diamino-diphenylmethane, 3,3′-diamino-diphenylmethane, 4,4′-diamino-diphenylsulfide, 3, 3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,3'-diamino-diphenyl sulfone, 4,4'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, benzidine, 3, 3'-diamino-biphenyl, 3,3'-dimethyl 4,4'-diamino biphenyl, 3,3'-dimethoxy - benzidine, 4,4 '- diamino -p- terphenyl, 3,3'-diamino -p- terphenyl,

Bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (1, -dimethyl-5) -Aminopentyl) benzene, 1,5-diamino-naphthalene, 2,6-diamino-naphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diamino-toluene, m-xylene- 2,5-diamine, p-xylene-2,5-diamine, m-xylylene-diamine, p-xylylene-diamine, 2,5-diamino-pyridine, 2,6-diamino-pyridine, 2,5-diamino- Pyridine, 2,5-diamino-1,3,4-oxadiazole, 1.4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamidine , Propylene - diamine, 2,2-dimethyl - propylene - diamine, tetramethylenediamine - diamine, pentamethylene - diamine, hexamethylene - diamine, 2,5-dimethyl - hexamethylene - diamine,

3-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl-heptamethylene-diamine, 3-methyl-heptamethylene-diamine, 4,4-dimethyl-heptamethylene-diamine, octamethylene-diamine, Nonamethylene-diamine, 5-methyl-nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, diamino-cyclohexane, 3,5-diaminobenzoic acid, 3,3′-diamino-4,4′- Carboxylic benzidine, o-tolidine, m-tolidine, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-amino) Phenoxy) biphenyl, 4,4′-bis (3-aminophenyl) Enoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenyl) benzene,
9,10-bis (4-aminophenyl) anthracene, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 1,1,1,3,3 , 3-Hexafluoro-2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3-amino-4 -Methylphenyl) propane, 1,4-bis (3-aminopropyldimethylsilyl) benzene, or some of the hydrogen atoms directly bonded to the aromatic ring of these aromatic diamines are methyl, ethyl, and halogen Although the thing substituted by group selected from group can be mentioned, It is not limited to these. Moreover, in using these, it may be individual or a mixture of 2 or more types.

Other than the above-mentioned aromatic diamines, diamines having at least one group selected from the group consisting of a divalent aliphatic group having 4 to 30 carbon atoms and a divalent silicon-containing group having 2 to 50 silicon atoms are preferable. .
Examples of the divalent aliphatic group having 4 to 30 carbon atoms include aliphatic diamines having an acyclic structure (hereinafter simply referred to as “aliphatic diamines”) or diamines having an alicyclic structure (hereinafter referred to as “aliphatic diamines”). And simply referred to as “alicyclic diamines”).

  Specific examples of the aliphatic diamines include ethylene glycol diamines such as bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, and bis (2-aminomethoxy) ethyl. ] Ether, bis [2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2 -Aminoethoxy) ethane, 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane, ethylene glycol bis (3-aminopropyl) ether , Diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) Ether, methylenediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamino Examples include octane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. These aliphatic diamines may be used alone or in combination of two or more.

  Specific examples of the alicyclic diamines include, for example, isophorone diamine, 4,4′-diaminodicyclohexylmethane, 1,8-diamino-p-menthane, 1,4-cyclohexanebis (methylamine), 1,3- Cyclohexanebis (methylamine), 2,5-diaminomethyl-bicyclo [2,2,2] octane, 2,5-diaminomethyl-7,7-dimethylbicyclo [2,2,1] heptane, 2,5- Diaminomethyl-7,7-difluorobicyclo [2,2,1] heptane, 2,5-diaminomethyl-7,7,8,8-tetrafluorobicyclo [2,2,2] octane, 2,5-diamino Methyl-7,7-bis (hexafluoromethyl) bicyclo [2,2,1] heptane, 2,5-diaminomethyl-7-oxabicyclo [2,2,1] hepta 2,5-diaminomethyl-7-thiabicyclo [2,2,1] heptane, 2,5-diaminomethyl-7-oxobicyclo [2,2,1] heptane, 2,5-diaminomethyl-7-azabicyclo [2,2,1] heptane,

2,6-diaminomethyl-bicyclo [2,2,2] octane, 2,6-diaminomethyl-7,7-dimethylbicyclo [2,2,1] heptane, 2,6-diaminomethyl-7,7- Difluorobicyclo [2,2,1] heptane, 2,6-diaminomethyl-7,7,8,8-tetrafluorobicyclo [2,2,2] octane, 2,6-diaminomethyl-7,7-bis (Hexafluoromethyl) bicyclo [2,2,1] heptane, 2,6-diaminomethyl-7-oxybicyclo [2,2,1] heptane, 2,6-diaminomethyl-7-thiobicyclo [2,2, 1] heptane, 2,6-diaminomethyl-7-oxobicyclo [2,2,1] heptane, 2,6-diaminomethyl-7-iminobicyclo [2,2,1] heptane, 2,5-diamino- Bisik [2,2,1] heptane, 2,5-diamino-bicyclo [2,2,2] octane, 2,5-diamino-7,7-dimethylbicyclo [2,2,1] heptane, 2,5- Diamino-7,7-difluorobicyclo [2,2,1] heptane,

2,5-diamino-7,7,8,8-tetrafluorobicyclo [2,2,2] octane, 2,5-diamino-7,7-bis (hexafluoromethyl) bicyclo [2,2,1] Heptane, 2,5-diamino-7-oxabicyclo [2,2,1] heptane, 2,5-diamino-7-thiabicyclo [2,2,1] heptane, 2,5-diamino-7-oxobicyclo [ 2,2,1] heptane, 2,5-diamino-7-azabicyclo [2,2,1] heptane, 2,6-diamino-bicyclo [2,2,1] heptane, 2,6-diamino-bicyclo [ 2,2,2] octane, 2,6-diamino-7,7-dimethylbicyclo [2,2,1] heptane, 2,6-diamino-7,7-difluorobicyclo [2,2,1] heptane, 2,6-diamino-7,7,8, -Tetrafluorobicyclo [2,2,2] octane, 2,6-diamino-7,7-bis (hexafluoromethyl) bicyclo [2,2,1] heptane, 2,6-diamino-7-oxybicyclo [ 2,2,1] heptane,

2,6-diamino-7-thiobicyclo [2,2,1] heptane, 2,6-diamino-7-oxobicyclo [2,2,1] heptane, 2,6-diamino-7-iminobicyclo [2, 2,1] heptane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) ) Cyclohexane, 1,4-di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5 , 5] undecane, bicyclo [2,2,1] heptanebismethylamine, and compounds represented by the following formula. These alicyclic diamines may be used alone or in combination of two or more.

（式中、Ｒ₇ およびＲ₁₀は二価の炭化水素基を示し、それぞれ同一でも異なっていてもよく、Ｒ₈ およびＲ₉ は一価の炭化水素基を示し、それぞれ同一でも異なっていてもよく、ｐは１以上の整数を表す。）
Ｒ₇ およびＲ₁₀の好ましい炭化水素基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、およびフェニレン基などを挙げることができる。またＲ₈ およびＲ₉ 基についての好適な例としては、メチル基、エチル基、プロピル基、ブチル基、およびフェニル基などを挙げることができる。 As the diamine having a divalent silicon-containing group having 2 to 50 silicon atoms (hereinafter simply referred to as “silicon-containing diamine”), for example, diamino (poly) siloxane represented by the following formula is preferably used. Can do.

(Wherein R ₇ and R ₁₀ represent a divalent hydrocarbon group, which may be the same or different, and R ₈ and R ₉ represent a monovalent hydrocarbon group, which may be the same or different, respectively. Well, p represents an integer of 1 or more.)
Preferred hydrocarbon groups for R ₇ and R ₁₀ include methylene group, ethylene group, propylene group, butylene group, and phenylene group. Preferred examples of the R ₈ and R ₉ groups include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.

R in the general formula (1) is a photosensitive group having a secondary carbon as a bonding point. As shown in the formula (3), one group separated from the secondary carbon is polymerized by actinic radiation. available carbon - have a monovalent organic group represented by a having one carbon double bond, the a, -Q'OC = OC (Q " ) = CH 2 (Q ' is CH _2, C ₂ H ₄ or an organic group having 3 to 12 carbon atoms. Q ″ is exemplified by H or —C ₃ ). On the other hand, B is a monovalent organic group. Examples of the group represented by B include —CH ₃ , —CH ₂ R ′ (R ′ is an acrylate group or a methacrylate group), or —CH ₂ OR ″ (R "is _{-CH 3, -C 3 H 10,} t- butyl group, a cyclohexyl group, a phenyl group, or a substituent selected from the number 1 to 12 of the organic group having a carbon) can be exemplified.
When the bond point is primary carbon, side reactions such as imidization easily occur in a composition with strong acidity or basicity, development time is long, and residual undissolved residue is generated. May get worse. When the attachment point is tertiary carbon, the reactivity becomes extremely low at the time of introduction, and it becomes difficult to incorporate it into the skeleton. Furthermore, the photosensitive group having a structure represented by the formula (3) can be easily introduced.

  Examples of the compound for introducing R include 2-hydroxypropyl-acrylate, 2-hydroxypropyl-methacrylate, 2-hydroxybutyl-acrylate, 2-hydroxybutyl-methacrylate, 2-hydroxy-3-methoxy. Propyl-acrylate, 2-hydroxy-3-methoxypropyl-methacrylate, 2-hydroxy-3-butoxypropyl-acrylate, 2-hydroxy-3-butoxypropyl-methacrylate, 2-hydroxy-3-phenoxypropyl-acrylate, 2- Hydroxy-3-phenoxypropyl-methacrylate, 2-hydroxy-3-t-butoxypropyl-acrylate, 2-hydroxy-3-t-butoxypropyl-methacrylate, 2-hydroxy-3-cyclo Xylalkoxypropyl-acrylate, 2-hydroxy-3-cyclohexyloxypropyl-methacrylate, 2-hydroxy-3-cyclohexyloxypropyl-acrylate, 2-methacryloxyethyl-2-hydroxypropyl phthalate, 2-acryloxyethyl-2- Examples thereof include, but are not limited to, hydroxypropyl phthalate, glycerin diacrylate, glycerin dimethacrylate, and the like. Moreover, in using these, it may be individual or a mixture of 2 or more types.

  In addition, a part of R in the general formula (1) may be a photosensitive group having a secondary carbon as a bonding point, for example, a photosensitive group having a primary carbon as a bonding point, or a tertiary carbon as a bonding point. It may be bonded to a photosensitive group having a saturated bonding group having primary, secondary and tertiary carbons as a bonding point, in which case 80% of the photosensitive group having a secondary carbon as a bonding point is used. Those containing above are preferred, those containing 90% or more are more preferred, and those containing 100% are most preferred.

(B) Photoinitiator The photopolymerization initiator used in the present invention is a compound having an absorption maximum wavelength (λmax) at 330 nm to 500 nm. It is preferable that this λmax is 330 nm or more because the polyamic acid ester itself does not absorb light. Further, it is preferable that λmax is 500 nm or more because no photoreaction occurs with visible light and handling properties do not deteriorate. For example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, fluorenone and other benzophenone derivatives, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropio Phenone, acetophenone derivatives such as 1-hydroxycyclohexyl phenyl ketone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, Benzoin derivatives such as benzoin and benzoin methyl ether, 2,6-di (4-azidobenzylidene) -4-methylcyclohexanone, 2,6′-di (4 Azides such as azidobenzylidene) cyclohexanone, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, 1,3-diphenyl-propanetrione- Examples include oximes such as 2- (o-ethoxycarbonyl) oxime and 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, but are not limited thereto. In use, it may be used alone or as a mixture of two or more. Among the above photopolymerization initiators, oximes are preferable from the viewpoint of photosensitivity.
The addition amount of these photopolymerization initiators is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the polyamic acid ester. When the amount added is more than 1 part by weight, the effect of improving the sensitivity is obtained, and when the amount added is less than 15 parts by weight, the strength of the cured film is improved, which is preferable.

(C) Solvent As the solvent that is a component of the polyamic acid ester composition of the present invention, a polar organic solvent is preferably used from the viewpoint of solubility in the components (A) and (B). Specifically, N, N-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone , Tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and the like, which can be used alone or in combination of two or more. .
These solvents can be used in the range of 30 to 600 parts by mass with respect to 100 parts by mass of the (A) polyamic acid ester, depending on the coating film thickness and viscosity.
Furthermore, in order to improve the storage stability of the polyamic acid ester composition of the present invention, it is preferable that an alcohol be included in the organic solvent used as the solvent.

The alcohol that can be used is not particularly limited as long as it has an alcoholic hydroxyl group in the molecule. Specific examples thereof include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and n-butyl. Lactic acid esters such as alcohol, isobutyl alcohol, t-butyl alcohol, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-2-methyl ether, propylene glycol-1-ethyl ether, propylene glycol-2-ethyl ether, Propylene glycol monoalkyl ethers such as propylene glycol-1- (n-propyl) ether and propylene glycol-2- (n-propyl) ether, ethylene glycol methyl ether, ethylene glycol ether Ether, mono-alcohols such as ethylene glycol -n- propyl ether, 2-hydroxyisobutyric acid esters, ethylene glycol, di alcohols such as propylene glycol, and the like. Among these, lactic acid esters, propylene glycol monoalkyl ethers, 2-hydroxyisobutyric acid esters, and ethyl alcohol are preferable. Particularly, ethyl lactate, propylene glycol-1-methyl ether, propylene glycol-1-ethyl ether, propylene Glycol-1- (n-propyl) ether is more preferred.
The alcohol content in the total solvent is preferably 5 to 50% by weight, more preferably 10 to 30% by weight. When the alcohol content is 5% by weight or more, the storage stability of the polyamic acid ester composition is improved. Moreover, when it is 50 weight% or less, the solubility of the polyamic acid ester which is (A) component becomes favorable.

(D) Other components A sensitizer for improving photosensitivity can be added to the photosensitive composition of the present invention as desired. Examples of such a sensitizer include Michler's ketone, 4,4′-bis (diethylamino) benzophenone, 2,5-bis (4′-diethylaminobenzylidene) cyclopentanone, and 2,6- (4′-diethylaminobenzylidene). ) Cyclohexanone, 2,6-bis (4′-dimethylaminobenzylidene) -4-methylcyclohexanone, 2,6-bis (4′-diethylaminobenzylidene) -4-methylcyclohexanone, 4,4′-bis (dimethylamino) Chalcone, 4,4′-bis (diethylamino) chalcone, 2- (4′-dimethylaminocinnamylidene) indanone, 2- (4′-dimethylaminobenzylidene) indanone, 2- (p-4′-dimethylaminobiphenyl) ) -Benzothiazole, 1,3-bis (4-dimethylaminobenzylidene) ) Acetone, 1,3-bis (4-diethylaminobenzylidene) acetone, 3,3′-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylamino Coumarin, 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N-ethylethanolamine, N-phenyldiethanolamine, N -P-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl 4-dimethylaminobenzoate, isoamyl 4-diethylaminobenzoate, 2-mercaptobenzimidazole, 1-pheny 5-mercapto-1,2,3,4-tetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p -Dimethylaminostyryl) naphtho (1,2, -d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, benzotriazole and the like. These are used singly or in combination of 2 to 5 kinds, and the addition amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyamic acid ester.

  If desired, an adhesion aid may be added to the photosensitive composition of the present invention to improve the adhesion to the substrate. Examples of such adhesion assistants include γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycid. Xylpropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycid Xylpropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide, N- [3- (triethoxysilyl) propyl] phthalamic acid, benzophenone-3,3′-bis (3-triethoxysilyl) propylamino Carbo Le-4,4'-dicarboxylic acid, benzene-1,4-bis (3-triethoxysilyl) propyl aminocarbonyl-2,5-dicarboxylic acid. These addition amounts are preferably in the range of 0.5 to 10 parts by weight with respect to 100 parts by weight of the polyamic acid ester.

  If desired, a thermal polymerization inhibitor can be added to the photosensitive composition of the present invention in order to improve the viscosity of the composition solution during storage and the stability of photosensitivity. Examples of such thermal polymerization inhibitors include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetrachloride. Acetic acid, 2,6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N -Ethyl-N-sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N (1-naphthyl) hydroxylamine ammonium salt Bis (4-hydro Shi -3,5-tert-butyl -. Phenyl methane is used the amount added is, with respect to the polyimide precursor 100 parts by weight, preferably in the range of 0.005 to 5 parts by weight.

  In addition, the reactive monomer in the liquid photosensitive resin composition used in the present invention is not particularly limited, but is one that undergoes radical polymerization reaction by the action of a photoradical generator, or the action of a photoacid generator or photobase generator. A ring-opening polymerization reaction can be selected. Although it does not specifically limit as a reactive monomer which carries out radical polymerization reaction, The mono- or diacrylate and methacrylate of ethylene glycol or polyethyleneglycol, including diethylene glycol and tetraethyleneglycol dimethacrylate, the mono- or diacrylate of propylene glycol or polypropylene glycol, or Diacrylate and methacrylate, mono-, di- or triacrylate and methacrylate of glycerol, cyclohexane diacrylate and dimethacrylate, diacrylate and dimethacrylate of 1,4-butanediol, diacrylate and dimethacrylate of 1,6-hexanediol, neo Pentyl glycol diacrylate and dimethacrylate,

Bisphenol A mono or diacrylate and methacrylate, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and derivatives thereof, methacrylamide and derivatives thereof, trimethylolpropane triacrylate and methacrylate, di or triacrylate and methacrylate of glycerol, penta Di, tri, or tetraacrylates and methacrylates of erythritol, and ethylene oxide or propylene oxide adducts of these compounds, methylene bisacrylamide, N-methylol acrylamide, ethylene glycol diglycidyl ether-methacrylic acid adduct, glycerol diglycidyl ether-acrylic Acid adduct, bisphenol A digly Jill ether - acrylic acid adduct, bisphenol A diglycidyl ether - but methacrylic acid adduct, but are not limited thereto. Moreover, in using these, it may be individual or a mixture of 2 or more types.
These compounds are preferably used by dissolving 1 to 100 parts by weight with respect to 100 parts by weight of the polyamic acid ester. If the amount of this compound is more than 1 part by weight, curing proceeds sufficiently during exposure, and if this amount does not exceed 100 parts by weight, the solution viscosity of the varnish does not decrease and a uniform coating film is obtained.

<Polyimide pattern forming method and semiconductor device>
The photosensitive composition of the present invention can be applied onto a substrate by, for example, a coating method using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, or the like, or a spray coating method using a spray coater. The obtained coating film is dried by air drying, heat drying by an oven or a hot plate, vacuum drying, or the like. The coating film thus obtained is exposed with an ultraviolet light source or the like using an exposure apparatus such as a contact aligner, mirror projection, or stepper. From the viewpoint of pattern resolution and handleability, the light source wavelength is preferably i-line, and a stepper is preferable as the exposure apparatus.
The developer used for development is preferably a good solvent for the polyamic acid ester composition or a combination of a good solvent and a poor solvent. As the good solvent, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and the like are preferable. Toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate and water are used. When a good solvent and a poor solvent are mixed and used, the ratio of the poor solvent to the good solvent is adjusted depending on the solubility of the polymer. Moreover, several types of solvents can be used in combination.

As a method used for development, an arbitrary method can be selected from conventionally known photoresist development methods such as a rotary spray method, a paddle method, and an immersion method involving ultrasonic treatment.
The polyamic acid ester pattern obtained as described above is heated to dilute the photosensitive component, and is converted into a polyimide pattern by polyimidation. Various methods such as a method using a hot plate, a method using an oven, and a method using a temperature rising oven capable of setting a temperature program can be selected as the method for heat curing. Heating can be performed at 250 to 450 ° C. for 30 minutes to 5 hours. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used.
In still another aspect of the present invention, a semiconductor device having a polyimide pattern formed by the above-described method is provided. The semiconductor device can be obtained by combining the above-described polyimide pattern forming method with a known method for manufacturing a semiconductor device.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these Examples.
In Examples, Comparative Examples and Reference Examples, the physical properties of the photosensitive polyamic acid ester composition were measured and evaluated according to the following methods.
(1) Weight average molecular weight The weight average molecular weight (Mw) of each polyamic acid ester was measured by the gel permeation chromatography method (standard polystyrene conversion).

(2) Evaluation of resolution of cured relief pattern The photosensitive resin composition was spin-coated on a 5-inch silicon wafer and dried to form a 10 μm thick coating film. This coating film was irradiated with energy of 400 mJ / cm ² using an i-line stepper NSR2005i8A (Nikon Corporation, Japan) using a reticle with a test pattern. Subsequently, the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate. A relief pattern was obtained.
The wafer on which the relief pattern was formed was heat-treated in a nitrogen atmosphere at 200 ° C. for 1 hour and subsequently at 350 ° C. for 2 hours using a temperature rising programmed curing furnace (VF-2000 type, manufactured by Koyo Lindberg, Japan). As a result, a cured relief pattern made of a polyimide resin having a thickness of about 5 μm was obtained on the silicon wafer.
About the obtained hardening relief pattern, the pattern shape and the width | variety of the pattern part were observed under the optical microscope, and the resolution was calculated | required. Regarding the resolution, a pattern having a plurality of openings with different areas is formed by the above method by exposing through a reticle with a test pattern, and the area of the resulting polyimide resin pattern opening is the corresponding pattern reticle opening. If the area is ½ or more of the area, it is regarded as resolved, and the length of the opening side of the reticle corresponding to the resolved opening having the smallest area is defined as the resolution. A resolution of 10 μm or less was considered good.

(3) Evaluation of sensitivity stability of photosensitive polyamic acid ester composition The photosensitive resin composition was spin-coated on a 5-inch silicon wafer and dried to form a coating film having a thickness of about 10 μm. The film thickness at this time was defined as T1. This coating film was irradiated with energy of 400 mJ / cm ² using an i-line stepper NSR2005i8A (Nikon Corporation, Japan) using a reticle with a test pattern. Subsequently, the coating film formed on the wafer is spray-developed with a developing machine (D-SPIN636 type, manufactured by Dainippon Screen Mfg. Co., Ltd.) using cyclopentanone as a developer, and rinsed with propylene glycol methyl ether acetate. A relief pattern was obtained. The film thickness after development was defined as T2. [T2 / T1] × 100 was defined as the remaining film ratio, and the sensitivity was defined by the remaining film ratio. If the remaining film ratio was 90% or more, it was determined to be acceptable.

(4) Evaluation of viscosity stability of photosensitive polyamic acid ester composition The photosensitive resin composition was subjected to a viscosity of 23 ° C. for 5 minutes using an E-type viscometer (RE-80R, manufactured by Tokyo Keiki Co., Ltd.). Measured below. The photosensitive resin composition was allowed to stand for 1 week and 2 weeks under conditions of a temperature of 23 ° C. and a humidity of 45%, and then the viscosity was measured under the same conditions. On the basis of the initial viscosity, if the rate of change in viscosity is ± 10% or less, it was judged as acceptable.

Reference Example 1 (Synthesis of polyamic acid ester A-1)
88.3 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) was placed in a 5 liter separable flask, 89.1 g of 2-hydroxypropyl methacrylate (HPMA) and 400 ml of γ-butyrolactone. The mixture was stirred at room temperature, and 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours. Next, a mixed liquid of 100.9 g of 5-amino-N- (N- (2-methacryloyloxyethyl) carbamoyl) isophthalic acid, 47.5 g of pyridine, and 200 ml of γ-butyrolactone was added.

Next, under ice cooling, a solution of 242.6 g of dicyclohexylcarbodiimide (DCC) dissolved in 240 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by bis [4- (4-aminophenoxy). A suspension of 210.3 g of phenyl] sulfone (BAPS) in 630 ml of γ-butyrolactone was added over 60 minutes with stirring. Furthermore, after stirring at 5 degreeC for 2 hours, the solution which melt | dissolved 70.9 g of silicone diamines (Azmax company make, FM3311, molecular weight 1000) in 140 g of diethylene glycol dimethyl ether was dripped over 20 minutes. After further stirring for 2 hours at room temperature, 60 ml of ethyl alcohol was added and stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 liter of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water to precipitate the polymer, and the resulting precipitate was filtered off and dried in vacuo to obtain a powdered polymer (polyamic acid ester A-1). . When the molecular weight of the polyamic acid ester A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 23,000.

Reference Example 2 (Synthesis of polyamic acid ester B-1)
The polyamic acid ester B-1 was reacted in the same manner as in Reference Example 1 except that 2-hydroxypropyl methacrylate (HPMA) of A-1 was changed to 80.4 g of 2-hydroxyethyl methacrylate (HEMA). Got. When the molecular weight of the polyamic acid ester B-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 24,000.

Reference Example 3 (Synthesis of polyamic acid ester A-2)
Place 124.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) in a 2 liter separable flask, add 115.3 g of 2-hydroxypropyl methacrylate (HPMA) and 400 ml of γ-butyrolactone, and stir at room temperature. While stirring, 63.3 g of pyridine was added to obtain a reaction mixture. After completion of the exothermic reaction, the mixture was allowed to cool to room temperature and left for 16 hours. Next, under ice-cooling, a solution obtained by dissolving 165.1 g of dicyclohexylcarbodiimide (DCC) in 200 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring. This reaction solution was added to a 5 liter separable flask in which 74.4 g of 4,4′-diaminodiphenyl ether (DADPE) was suspended in 200 ml of γ-butyrolactone with stirring in ice cooling over 60 minutes.
After further stirring at room temperature for 4 hours, 240 ml of ethyl alcohol was added and stirred for 1 hour, and then 7000 ml of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was added to 10 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer. The produced crude polymer was separated by filtration and dissolved in 1.5 L of NMP to obtain a crude polymer solution. The crude polymer solution was dropped into 28 liters of water to precipitate a polymer, and the resulting precipitate was filtered off and dried under vacuum to obtain a powdery polymer (polyamic acid ester A-2). It was 18000 when the weight average molecular weight (Mw) of polyamic acid ester A-2 was measured by the gel permeation chromatography (standard polystyrene conversion).

Reference Example 4 (Synthesis of polyamic acid ester B-2)
The polyamic acid ester B-2 was reacted by the same method as in Reference Example 1 except that 2-hydroxypropyl methacrylate (HPMA) of A-1 was changed to 107.2 g of 2-hydroxyethyl methacrylate (HEMA). Got. When the molecular weight of the polyamic acid ester B-2 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 24,000.

Reference Example 5 (Synthesis of polyamic acid ester A-3)
As in Reference Example 1, except that 87.2 g of pyromellitic dianhydride (PMDA) was used as the tetracarboxylic acid and 84.1 g of 3,3′-dimethyl-4,4′-diaminodiphenylmethane was used as the diamine. Reaction was performed to obtain polyamic acid ester A-3. When the molecular weight of the polyamic acid ester A-3 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 28,000.

Reference Example 6 (Synthesis of polyamic acid ester B-3)
2-hydroxypropyl of A-3 using 87.2 g of pyromellitic dianhydride (PMDA) as tetracarboxylic acid and 84.1 g of 3,3′-dimethyl-4,4′-diaminodiphenylmethane as diamine. A polyamic acid ester B-3 was obtained by reacting in the same manner as in Reference Example 1, except that the methacrylate (HPMA) was changed to 107.2 g of 2-hydroxyethyl methacrylate (HEMA). When the molecular weight of the polyamic acid ester B-3 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 28,000.

Reference Example 7 (Synthesis of polyamic acid ester A-4)
Reference Example, except that 124.1 g of 4,4′-oxydiphthalic dianhydride (ODPA) was used as the tetracarboxylic acid and 84.1 g of 3,3′-dimethyl-4,4′-diaminodiphenylmethane was used as the diamine. 1 to obtain a polyamic acid ester A-4. When the molecular weight of the polyamic acid ester A-4 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 25,000.

Reference Example 8 (Synthesis of polyamic acid ester B-4)
Using 44.1 'of 4,4'-oxydiphthalic dianhydride (ODPA) as tetracarboxylic acid and 84.1 g of 3,3'-dimethyl-4,4'-diaminodiphenylmethane as diamine, A polyamic acid ester B-4 was obtained by reacting in the same manner as in Reference Example 1 except that 2-hydroxypropyl methacrylate (HPMA) was changed to 107.2 g of 2-hydroxyethyl methacrylate (HEMA). When the molecular weight of the polyamic acid ester B-4 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 25,000.

Reference Example 9 (Synthesis of polyamic acid ester A-5)
Using 94.2 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride (BPDA) as tetracarboxylic acid and 84.1 g of 3,3′-dimethyl-4,4′-diaminodiphenylmethane as diamine The polyamic acid ester A-5 was obtained by reacting in the same manner as in Reference Example 1 except that. When the molecular weight of the polyamic acid ester A-5 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 23,000.

Reference Example 10 (Synthesis of polyamic acid ester B-5)
94.2 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride (BPDA) was used as the tetracarboxylic acid and 84.1 g of 3,3′-dimethyl-4,4′-diaminodiphenylmethane was used as the diamine. Then, except that A-5 2-hydroxypropyl methacrylate (HPMA) was changed to 107.2 g of 2-hydroxyethyl methacrylate (HEMA), the reaction was carried out in the same manner as in Reference Example 1 to obtain a polyamic acid ester B-5. . When the molecular weight of the polyamic acid ester B-5 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 23,000.

[Example]
Using the polyamic acid esters (A-1 to A-5, B-1 to B-5) obtained in the above Reference Examples 1 to 10, a photosensitive polyamic acid ester composition was prepared and adjusted by the following method. The composition was evaluated. 100 g of polyamide acid ester (A-1 to A-5, B-1 to B-5), 4 g of 1,3-diphenylpropanetrione-2- (o-phenylcarbonyl) oxime (photoinitiator), tetraethylene glycol It consists of 80 g of NMP and 20 g of ethyl lactate together with 4 g of dimethacrylate, 2 g of benzotriazole, 4 g of N-phenyldiethanolamine, 3 g of N- [3- (triethoxysilyl) propyl] phthalamic acid, and 0.02 g of 2-nitroso-1-naphthol. Dissolved in the mixed solvent. The viscosity of the obtained solution was adjusted to about 40 poise by further adding a small amount of the mixed solvent to obtain a photosensitive polyamic acid ester composition.
The development residual film rate test and the viscosity increase rate test were performed on the photosensitive polyamic acid ester composition by the methods described above. The results are shown in Table 1.

  The composition of the present invention can be suitably used in the field of photosensitive materials useful for the production of electrical / electronic materials such as semiconductor devices and multilayer wiring boards. More specifically, the composition of the present invention can be suitably used as a photosensitive polyamic acid ester composition capable of providing a polyimide pattern having excellent stability over time even at room temperature, regardless of the composition.

Claims (5)

(A) 100 parts by mass of a polyamic acid ester having a weight average molecular weight of 8000 to 150,000 consisting of a repeating unit represented by the following general formula (1), (B) 1 to 15 parts by mass of a photoinitiator, and (C) a solvent 30 A photosensitive polyamic acid ester composition comprising -600 parts by mass.

[Wherein, X represents a tetravalent organic group, and X ′ represents a divalent organic group selected from the group represented by the following formula (2). Y and Y ′ represent a divalent organic group, and R represents a monovalent photosensitive group having a secondary carbon having a structure represented by the following formula (3) as a bonding point. M is a positive integer, n is 0 or a positive integer, and 0.5 ≦ m / (m + n) ≦ 1.0.

(In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₆ are monovalent organic groups, and R ₅ is a divalent organic group. In addition, on the aromatic ring in formula (2) The hydrogen atom is at least one group selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a fluorine atom, and a trifluoromethyl group. It may be replaced.)

(A represents a monovalent organic group containing a carbon-carbon double bond polymerizable by actinic radiation, and B represents a monovalent organic group.)] The photosensitive polyamic acid ester composition according to claim 1, wherein the polyamic acid ester is composed of a repeating unit represented by the following general formula (4).

[Wherein, X represents a tetravalent organic group, Y represents a divalent organic group, and R represents a photosensitive group having a secondary carbon having a structure represented by the following formula (3) as a bonding point.

(A represents a monovalent organic group containing a carbon-carbon double bond polymerizable by actinic radiation, and B represents a monovalent organic group.)] The photosensitive polyamic acid ester composition according to claim 2, wherein the polyamic acid ester comprises a repeating unit represented by the following general formula (5).

[Wherein X ″ is a tetravalent organic group, Y ″ is a divalent organic group represented by the following general formula (6), and R is a secondary carbon having a structure represented by the following formula (3). The photosensitive group possessed as

(In the formula, A ′ represents a divalent aliphatic group, B ′ represents a monovalent aliphatic group, and D represents hydrogen or a monovalent aliphatic group.)

(A represents a monovalent organic group containing a carbon-carbon double bond polymerizable by actinic radiation, and B represents a monovalent organic group.)]   (1) The photosensitive polyimide acid ester composition according to any one of claims 1 to 3 is formed on a substrate in the form of a layer or a film, and (2) is exposed with actinic radiation through a mask, A method for producing a cured relief pattern, comprising directly irradiating a light beam, an electron beam or an ion beam, (3) eluting or removing an exposed portion or an irradiated portion, and (4) heat-treating the obtained relief pattern. A semiconductor device comprising a cured relief pattern layer obtained by the method for producing a cured relief pattern according to claim 4.