JP5111234B2 - Negative photosensitive resin composition capable of alkali development - Google Patents

Description

  The present invention relates to a negative photosensitive resin composition that can be alkali-developed and has no problem of metal corrosion when used for an insulating film of a semiconductor or a wiring board.

As a photosensitive heat-resistant material for mounting materials, a negative photosensitive polyimide that can be solvent-developed has been well known (see Non-Patent Document 1). On the other hand, photosensitive polybenzoxazole precursors that can be developed with an aqueous alkali solution have been widely used in recent years. Photosensitive polyimides and photosensitive polybenzoxazoles are widely used as semiconductor protective films and wiring interlayer insulating films (see Non-Patent Document 2).
As one of photosensitive polybenzoxazoles, a mixture of poly (o-hydroxyamide), a photoacid generator, and a crosslinkable compound or a dissolution inhibitor has been proposed (Non-Patent Documents 3 and 4).
However, the photoacid generator remains in the pattern formed in this manner, and there is a possibility that acid is generated in the process of thermosetting and converting the polymer into a heat-resistant polybenzoxazole skeleton.
In general, since the surface protective film and the interlayer insulating film are in contact with a metal such as copper or aluminum, it is considered that there is a problem that the metal is corroded by this acid during a reliability test or use.

Ueda, "Photosensitive polyimide", Journal of the Japan Society of Photography, Japan Society for Photography, 2003-06, 4, p367-375 Ikeda, Mizuno, “Photosensitive resin learned from the beginning”, Industrial Research Committee, April 10, 2002, p125-142 K. Fukukawa, and M.M. Ueda, Polym. J, 2006, 38, p405 K. Fukukawa, Y. et al. Shibasaki, and M.S. Ueda, Polym. J, 2004, 36, p489

  The negative photosensitive resin composition of the present invention is intended to provide a negative photosensitive resin composition that has lithographic performance and does not generate an acid during thermosetting, and thus has no problem of metal corrosion. It is.

  The present inventor has found that a negative photosensitive resin composition that solves the above problems can be obtained by combining a mixture of polyhydroxyamide and an ester compound with a compound that generates a base upon irradiation with active actinic radiation, The present invention has been accomplished.

That is, the present invention is as follows.
1. (A) Polyhydroxyamide having a repeating unit represented by the following general formula (I): 100 parts by mass, (B) Ester compound represented by the following general formula (II): 1-50 parts by mass, (C) A negative photosensitive resin composition comprising: a photobase generator: 2 to 30 parts by mass.
Wherein X ₁ is a tetravalent organic group having 2 or more carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having 2 or more carbon atoms. M is an integer of 2 to 200, n is an integer of 0 to 200, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ And the order of arrangement of n diamide units including X ₂ and Y ₂ is not limited.)
(In the formula, X is a monovalent to tetravalent aliphatic group having 1 to 4 carbon atoms, Z is hydrogen or an electron withdrawing group, p is an integer of 1 to 5, and q is an integer of 1 to 4.)

2. (B) The negative photosensitive resin composition as described in 1 above, wherein Z in the ester compound represented by the general formula (II) is an electron withdrawing group.
3. (B) The negative photosensitive resin composition as described in 1 or 2 above, wherein q in the ester compound represented by the general formula (II) is 2 to 4.
4). (C) The photobase generator is a compound that generates a secondary amine having at least one substituent at the α-position upon irradiation with actinic rays. Negative photosensitive resin composition.
5. 5. The negative photosensitive resin composition as described in 4 above, wherein the secondary amine has a cyclic structure.

6). 5. The negative photosensitive resin composition as described in 4 above, wherein the secondary amine is a compound represented by the following general formula (III).
(In formula, R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > may each independently have hydrogen, the C1-C6 alkyl group which may have a substituent, and a substituent. A cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms which may have a substituent, an alkene group having 1 to 6 carbon atoms which may have a substituent, and a substituent. An alkynyl group having 1 to 6 carbon atoms, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent (wherein R ₁ , R ₂ , At least one of R ₃ and R ₄ is not hydrogen), R ₅ and R ₆ are each independently hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a substituent. A C3-C8 cycloalkyl group which may have a C 1-6 alkyl which may have a substituent A xyl group, an optionally substituted alkene group having 1 to 6 carbon atoms, an optionally substituted alkynyl group having 1 to 6 carbon atoms, and an optionally substituted aryl group , A heterocyclic group which may have a substituent, a monocycle which may have a substituent formed by bonding to each other, or a substituent which may be formed by bonding to each other Indicates a polycycle.)

7). (C) The negative photosensitive resin composition as described in 1 above, wherein the photobase generator is a compound represented by the following general formula (IV).
(In the formula, R ₇ represents a nitrophenyl group which may have a substituent, and R ₈ and R ₉ each independently represent hydrogen or a C 1-6 which may have a substituent. of an alkyl _group, R 1 to R ₆ are as defined for _R 1 to R ₆ in the general formula (III).)

8). 8. The negative photosensitive resin composition as described in 7 above, wherein the compound represented by the general formula (IV) is a compound represented by the following general formula (V).
(In the formula, R ₁₀ has an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and a substituent. An optionally substituted alkoxyl group having 1 to 6 carbon atoms, an alkene group having 1 to 6 carbon atoms which may have a substituent, an alkynyl group having 1 to 6 carbon atoms which may have a substituent, and a substituent An aryl group that may have a substituent, a heterocyclic group that may have a substituent, a monocyclic ring that may have a substituent formed by bonding adjacent R _{10 to} each other, or an adjacent group R ₁₀ represents a polycycle which may have a substituent formed by bonding each other, and R ₈ and R ₉ are each independently hydrogen or a carbon which may have a substituent. 1 represents an alkyl group of 1 to 6 (provided that at least one of R ₈ and R ₉ is hydrogen), and s is 0 -4 represents an integer, and R _{1 to} R ₆ have the same meaning as R _{1 to} R ₆ in the general formula (III).

9. 8. The negative photosensitive resin composition as described in 7 above, wherein the compound represented by the general formula (IV) is a compound represented by the following general formula (VI).
(In the formula, R ₈ and R ₉ each independently represent hydrogen or an optionally substituted alkyl group having 1 to 6 carbon atoms (provided that at least one of R ₈ and R ₉ is Are hydrogen), R ₁₁ and R ₁₂ represent an optionally substituted alkoxyl group having 1 to 6 carbon atoms, t represents 0, 1 or 2, and R _{1 to} R ₄ represent the above general formulas. (It has the same meaning as R _{1 to} R ₄ in formula (III).)

10. (1) The process of forming the photosensitive resin layer which consists of a negative photosensitive resin composition as described in any one of said 1-9 on a board | substrate, (2) The process of exposing with an actinic ray through a mask, (3) a step of heating at 120 to 190 ° C., (4) a step of eluting or removing an unexposed portion with an alkaline aqueous solution, and (5) a step of heat-treating the obtained relief pattern. A method for producing a relief pattern.
11. 11. A semiconductor device having a cured relief pattern obtained by the production method described in 10 above.

The basic principle of lithographic performance in the photosensitive resin composition of the present invention is that the base produced by exposure serves as a catalyst, and the hydroxy group of polyhydroxyamide is esterified to reduce the solubility in an alkaline developer. is there.
To provide a photosensitive resin composition that does not generate acid when forming a cured relief pattern having a heat-resistant polybenzoxazole skeleton after exposure and development, and that does not have a problem that the metal underlying the relief pattern is corroded. Can do.

<Negative photosensitive resin composition>
Each component which comprises the negative photosensitive resin composition of this invention is demonstrated concretely below.
(A) Polyhydroxyamide Polyhydroxyamide, which is the base polymer of the negative photosensitive resin composition, has a repeating unit represented by the following general formula (I).
Wherein X ₁ is a tetravalent organic group having 2 or more carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having 2 or more carbon atoms. M is an integer of 2 to 200, n is an integer of 0 to 200, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ And the order of arrangement of n diamide units including X ₂ and Y ₂ is not limited.)
X ₁ is preferably a tetravalent organic group having 2 or more and 30 or less carbon atoms. X ₂ , Y ₁ and Y ₂ are preferably each independently a divalent organic group having 2 or more and 30 or less carbon atoms.

The dihydroxydiamide unit in the general formula (I) will be described. The dihydroxydiamide unit has a structure obtained by polycondensing a dicarboxylic acid having a Y ₁ (COOH) ₂ structure and a bisaminophenol having a X ₁ (NH ₂ ) ₂ (OH) ₂ structure. The two amino groups and the hydroxy group of the bisaminophenol are each in the ortho position, and the polyhydroxyamide is closed by heating to about 200 to 400 ° C. Change to benzoxazole.
m is preferably in the range of 2 to 200, more preferably in the range of 2 to 100, and most preferably in the range of 3 to 50.

The polyhydroxyamide represented by the general formula (I) has a structure having n diamide units. The diamide unit has a structure obtained by polycondensing a diamine having a structure of X ₂ (NH ₂ ) ₂ and a dicarboxylic acid having a structure of Y ₂ (COOH) ₂ . n is preferably in the range of 0 to 200, more preferably in the range of 0 to 100, and most preferably in the range of 0 to 50.
The higher the ratio of the above-mentioned dihydroxydiamide units in the polyhydroxyamide structure, the better the solubility in an alkaline aqueous solution used as a developer, so the value of m / (m + n) is preferably 0.5 or more, It is more preferably 0.7 or more, and most preferably 0.8 or more.

Examples of the bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ include 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, and 4,4 ′. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino- 4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis -(4-amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis -(4-amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino- 3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

Among these bisaminophenols having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , particularly preferred is the case where X ₁ is an aromatic group selected from the following.

In addition, as a compound having a structure of X ₁ (NH ₂ ) ₂ (OH) ₂ , two pairs of diamines having an amide bond and a phenolic hydroxyl group in the ortho position relative to each other (hereinafter referred to as “PBO precursor in the molecule”). Also referred to as “diamine having a structure”). For example, a diamine represented by the following general formula (VII) obtained by reacting bisaminophenol having the structure of X ₁ (NH ₂ ) ₂ (OH) ₂ with two molecules of nitrobenzoic acid and reducing the bisaminophenol is reduced. Can be mentioned.
(In the formula, X ₃ is a tetravalent organic group having at least 2 and not more than 15 carbon atoms, and at least one organic group selected from the group consisting of preferable organic groups represented by X ₁ described above. Preferably a group.)

As another method for obtaining a diamine having a PBO precursor structure in the molecule, dicarboxylic acid dichloride having a structure of Y ₃ (COCl) ₂ is reacted with two molecules of nitroaminophenol for reduction, and the following general formula (VIII) There is also a method for obtaining a diamine represented by
(In the formula, Y ₃ is a divalent organic group having at least 2 and not more than 15 carbon atoms, and at least one organic group selected from the group consisting of preferable organic groups represented by Y ₁ described later) Preferably a group.)

Examples of the diamine having the structure of X ₂ (NH ₂ ) ₂ include aromatic diamine and silicon diamine.
Among these, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′- Diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,2′-bis (4-aminophenyl) ) Propane, 2,2'-bis (4-aminophenyl) hexa Fluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene, 4-methyl-2,4-bis (4-aminophenyl) -2-pentene, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene, Imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis (4-aminophenyl) pentane, 5 (or 6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane, bis (p-aminophenyl) phosphine oxide, 4,4′-diaminoazobenzene, 4,4′-diamino Phenylurea, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 4,4'-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] benzophenone, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone, 4,4′-diaminobiphenyl, 4,4 '-Diaminobenzophenone, phenylindanediamine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4- (4-amino) Phenoxyphenyl) benzene, 1,3- (4-aminophenoxyphenyl) benzene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-di- (3-aminophenoxy) diphenylsulfone, and 4, 4′-diaminobenzanilide and the like, and the hydrogen atom of the aromatic nucleus of these aromatic diamines is at least selected from the group consisting of a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group A compound substituted by a kind of group or atom is mentioned.

Moreover, in order to improve adhesiveness with a base material, silicon diamine can be selected as a part or all of the diamine having the structure of X ₂ (NH ₂ ) ₂ , and examples thereof include bis (4-amino Phenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (4-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetramethyldisiloxane, 1,4-bis (γ-aminopropyl) Dimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, and the like.

Examples of the dicarboxylic acid having a Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structure include dicarboxylic acids in which Y ₁ and Y ₂ are each an aromatic group or an aliphatic group selected from the following.
Wherein A is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —, and a single bond. R represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an unsaturated group, and a halogen atom, and k represents each independently 0 to 4 Indicates an integer.)

In addition, a derivative of 5-aminoisophthalic acid can be used for a part or all of the dicarboxylic acid having the Y ₁ (COOH) ₂ and Y ₂ (COOH) ₂ structures. Specific compounds to be reacted with 5-aminoisophthalic acid to obtain the derivative 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, citraconic anhydride, itaconic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, allyl succinic anhydride , Isocyanate ethyl methacrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate 3-cyclohexene-1-carboxylic acid chloride, 2-furancarboxylic acid chloride, crotonic acid chloride, cinnamic acid chloride, methacrylic acid chloride, acrylic acid chloride, propiolic acid chloride, tetrolic acid chloride, thiophene 2-acetyl chloride, p -Styrenesulfonyl chloride, glycidyl methacrylate, allyl glycidyl ether, chloroformate methyl ester, chloroformate ethyl ester, chloroformate n-propyl ester, chloroformate isopropyl ester, chloroformate isobutyl ester, 2-ethoxy chloroformate Ester, chloroformate-sec-butyl ester, chloroformate benzyl ester, chloroformate 2-ethylhexyl ester, chloroformate allyl ester, chloroformate phenyl ester, chloro Acid 2,2,2-trichloroethyl ester, chloroformate-2-butoxyethyl ester, chloroformate-p-nitrobenzyl ester, chloroformate-p-methoxybenzyl ester, isobornylbenzyl chloroformate, Chloroformic acid-p-biphenylisopropylbenzyl ester, 2-t-butyloxycarbonyl-oxyimino-2-phenylacetonitrile, St-butyloxycarbonyl-4,6-dimethyl-thiopyrimidine, di-tert-butyl-dicarbonate N-ethoxycarbonylphthalimide, ethyldithiocarbonyl chloride, formic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, methanesulfonic acid chloride, acetyl chloride, trityl chloride, trimethylchlorosilane, hexamethyldisila N, O-bis (trimethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, (N, N-dimethylamino) trimethylsilane, (dimethylamino) trimethylsilane, trimethylsilyldiphenylurea, bis (trimethylsilyl) urea, isocyanic acid Examples include phenyl, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, cis-1,2-cyclohexanedicarboxylic anhydride, and glutaric anhydride.

Furthermore, as a dicarboxylic acid having a Y ₁ (COOH) _{2 or} Y ₂ (COOH) ₂ structure, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monoalcohol or a monoamine can also be used. Examples of monoalcohol include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and benzyl alcohol. Examples of monoamine include butylamine and aniline. As an example of said tetracarboxylic dianhydride, the compound shown by following Chemical formula is mentioned.
Wherein B is selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, and —C (CF ₃ ) ₂ —. Means a valent group.)
Alternatively, tetracarboxylic dianhydride can be reacted with bisaminophenol or diamine, and the resulting carboxylic acid residue can be esterified or amidated with a monoalcohol or monoamine.

Also, trimellitic acid chloride is reacted with bisaminophenol to produce tetracarboxylic dianhydride, and ring-opened in the same manner as the above tetracarboxylic dianhydride and used as dicarboxylic acid You can also. The tetracarboxylic dianhydride obtained here includes a chemical formula represented by the following general formula (IX).
(In the formula, X ₄ represents a divalent organic group represented by X ₁ (OH) ₂ (NH—) ₂ , and X ₁ represents the same organic group as X ₁ in the general formula (I)).

  As a method of polycondensation of the dicarboxylic acid and bisaminophenol (diamine) for synthesizing a polyhydroxyamide having a repeating unit represented by the above general formula (I), dicarboxylic acid and thionyl chloride are used. Examples thereof include a method in which bisaminophenol (diamine) is allowed to act after forming diacid chloride, or a method in which dicarboxylic acid and bisaminophenol (diamine) are polycondensed with dicyclohexylcarbodiimide. In the method using dicyclohexylcarbodiimide, hydroxybenztriazole can be allowed to act simultaneously.

  In the polyhydroxyamide having the repeating unit represented by the above general formula (I), the terminal group is used after being sealed with an organic group reactive with the terminal group (hereinafter also referred to as “sealing group”). It is also preferable. In the polycondensation of polyhydroxyamide, when the dicarboxylic acid component is used in an excessive number of moles compared to the sum of the bisaminophenol component and the diamine component, the compound having an amino group or a hydroxyl group is used as the blocking group. It is preferable to use it. Examples of the compound include aniline, ethynylaniline, norborneneamine, butylamine, propargylamine, ethanol, propargyl alcohol, benzyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate.

  Conversely, when the sum of the bisaminophenol component and the diamine component is used in an excessive number of moles compared to the dicarboxylic acid component, the sealing group has an acid anhydride, carboxylic acid, acid chloride, isocyanate group, etc. It is preferable to use a compound. Examples of such compounds include benzoyl chloride, norbornene dicarboxylic anhydride, norbornene carboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, maleic anhydride, phthalic anhydride, cyclohexane dicarboxylic anhydride, methyl cyclohexane dicarboxylic anhydride Products, cyclohexene dicarboxylic acid anhydride, methacryloyloxyethyl methacrylate, phenyl isocyanate, methanesulfonyl chloride, and p-toluenesulfonyl chloride.

  (A) The weight average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter also referred to as “GPC”) of polyhydroxyamide having a repeating unit represented by the above general formula (I) is 3,000 to 50,000. And preferably 6,000 to 30,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the cured relief pattern. Moreover, from a viewpoint of resolution, 50,000 or less is preferable. As developing solvents for GPC, tetrahydrofuran (hereinafter also referred to as “THF”) and N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) are recommended. The molecular weight is determined from a calibration curve prepared using standard monodisperse polystyrene. As the standard monodisperse polystyrene, it is recommended to select from organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko.

(B) Ester Compound As the ester compound, an ester compound represented by the following general formula (II) is used.
(In the formula, X is a monovalent to tetravalent aliphatic group having 1 to 4 carbon atoms, Z is hydrogen or an electron withdrawing group, p is an integer of 1 to 5, and q is an integer of 1 to 4.)
Among these, those in which Z is an electron withdrawing group are preferable. Specific examples of the electron withdrawing group include fluorine, chlorine, bromine, CF ₃ , cyano group, and nitro group. Of these, preferred are nitro group, cyano group and fluorine. From the viewpoint of sensitivity, it is preferable that q of the ester compound represented by the general formula (II) is 2 or more and 4 or less.

Specifically, in the above general formula (II), q = 1 is represented by the following formula, and Z is selected from hydrogen, nitro group, cyano group, and fluorine. Note that the electron-withdrawing group sigma _p substituent constant refers to positive ones. Substituent constants are described in Chemical Handbook Basics, revised edition 3 (issued June 25, 1984) p365.
As q = 2, it is shown by the following formula,

(Where r is an integer from 1 to 12)
Examples of q = 3 include those represented by the following formula.

(B) The addition amount of an ester compound is 1-50 mass parts with respect to 100 mass parts of (A) polyhydroxyamide, Preferably it is 3-30 mass parts, More preferably, it is 5-15 mass parts. Here, when the amount of the (B) ester compound added is 1 part by mass or more, the resolution is good, and when it is 50 parts by mass or less, the physical properties after thermosetting are good.

(C) Photobase generator (C) As a photobase generator, the compound which generate | occur | produces a base by irradiation of actinic light can be used. Examples thereof include cobalt amine complexes such as benzyl carbamate, benzyl sulfonamide, benzyl quaternary ammonium salt, oxime ester, nifedipine, α-aminoacetophenone, imine, iminium salt, triphenylsulfonium compound, cobalt amine perchlorate. Among these, a compound that generates a secondary amine having at least one substituent at the α-position is preferable. By using a compound that generates a secondary amine having at least one substituent at the α-position, the generated amine can be prevented from nucleophilic attack on the polyamic acid and other additives. As a result, generation of side reactions can be suppressed and partial imidization can be efficiently promoted. From the viewpoint of increasing basicity, the α-position substituent is preferably an electron-donating group. The electron donating group refers to those having a negative substituent constant σ _p . Substituent constants are described in Chemical Handbook Basics, revised edition 3 (issued June 25, 1984) p365.

  From the viewpoint of increasing the basicity, the secondary amine generated by irradiation with actinic rays preferably has a cyclic structure. In the present invention, “secondary amine has a cyclic structure” means that a heterocyclic structure containing a nitrogen atom of the secondary amine exists, and a cyclic structure not containing a nitrogen atom of the secondary amine. Does not mean. Here, the active light means visible light, ultraviolet light, electron beam, X-ray or the like. In particular, ultraviolet rays of 365 nm and 435 nm are preferable.

The secondary amine obtained by irradiating the photobase generator with actinic rays is preferably a compound represented by the following general formula (III).
(In formula, R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > may each independently have hydrogen, the C1-C6 alkyl group which may have a substituent, and a substituent. A cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms which may have a substituent, an alkene group having 1 to 6 carbon atoms which may have a substituent, and a substituent. An alkynyl group having 1 to 6 carbon atoms, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent (wherein R ₁ , R ₂ , At least one of R ₃ and R ₄ is not hydrogen), R ₅ and R ₆ are each independently hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a substituent. A C3-C8 cycloalkyl group which may have a C 1-6 alkyl which may have a substituent A xyl group, an optionally substituted alkene group having 1 to 6 carbon atoms, an optionally substituted alkynyl group having 1 to 6 carbon atoms, and an optionally substituted aryl group , A heterocyclic group which may have a substituent, a monocycle which may have a substituent formed by bonding to each other, or a substituent which may be formed by bonding to each other Indicates a polycycle.)
Any substituent may be used as long as it does not contradict the spirit of the present invention.

Preferable examples of the photobase generator according to the present invention include compounds represented by the following general formula (IV), specifically those having a benzyl carbamate structure, benzoin compounds, and the like.
(In the formula, R ₇ represents a nitrophenyl group which may have a substituent, and R ₈ and R ₉ each independently represent hydrogen or a C 1-6 which may have a substituent. of an alkyl _group, R 1 to R ₆ are as defined for _R 1 to R ₆ in the general formula (III).)
As the nitrophenyl group which may have the above-mentioned substituent, it is preferable that the R ₇ —H compound has an absorption maximum at a wavelength of 230 to 450 nm. In order to form a relief pattern, which will be described later, using i-line with a wavelength of 365 nm, it is preferable to have an absorption maximum at 310 to 390 nm, and an absorption maximum at 330 to 370 nm. Further preferred.

Particularly preferred examples of the photobase generator include compounds represented by the following general formula (V), specifically, compounds having an ortho-nitrobenzene structure.
(In the formula, R ₁₀ has an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and a substituent. An optionally substituted alkoxyl group having 1 to 6 carbon atoms, an alkene group having 1 to 6 carbon atoms which may have a substituent, an alkynyl group having 1 to 6 carbon atoms which may have a substituent, and a substituent An aryl group that may have a substituent, a heterocyclic group that may have a substituent, a monocyclic ring that may have a substituent formed by bonding adjacent R _{10 to} each other, or an adjacent group R ₁₀ represents a polycycle which may have a substituent formed by bonding each other, and R ₈ and R ₉ are each independently hydrogen or a carbon which may have a substituent. 1 represents an alkyl group of 1 to 6 (provided that at least one of R ₈ and R ₉ is hydrogen), and s is 0 -4 represents an integer, and R _{1 to} R ₆ have the same meaning as R _{1 to} R ₆ in the general formula (III).
In this case, at least one of R ₈ and R ₉ is hydrogen. This is because by having an ortho-nitrobenzyl structure, hydrogen extraction at the benzyl position by light irradiation occurs, followed by elimination of nitrosaldehyde and carbon dioxide, whereby a base can be generated efficiently.

As a preferable example of a photobase generator when the actinic ray wavelength is 365 nm i-line, a compound represented by the following general formula (VI) can be exemplified.
(In the formula, R ₈ and R ₉ each independently represent hydrogen or an optionally substituted alkyl group having 1 to 6 carbon atoms (provided that at least one of R ₈ and R ₉ is Are hydrogen), R ₁₁ and R ₁₂ represent an optionally substituted alkoxyl group having 1 to 6 carbon atoms, t represents 0, 1 or 2, and R _{1 to} R ₄ represent the above general formulas. (It has the same meaning as R _{1 to} R ₄ in formula (III).)

Specific examples of the compound represented by the general formula (VI) include N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -diisopropylamine, N-{[(4,5- Dimethoxy-2-nitrobenzyl) oxy] carbonyl} -bis (3-pentyl) amine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -bis (4-heptyl) amine, N -{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -dicyclopropylamine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -dicyclobutylamine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -dicyclopentylamine, N-{[(4,5-dimethoxy-2- Trobenzyl) oxy] carbonyl} -dicyclohexylamine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine (hereinafter also referred to as DNCDP), N-{[(4 , 5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpyrrolidine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethyl-4 -Methyl-piperazine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylmorpholine, N-{[(4,5-dimethoxy-2-nitrobenzyl) oxy ] Carbonyl} -2,6-dimethylthiomorpholine, N-{[(3,4-dimethoxy-2-nitrobenzyl) oxy] Rubonyl} -2,6-dimethylpiperidine, N-{[(3,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine, N-{[(3,6-dimethoxy-2 -Nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine, N-{[(4,6-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine, N-{[(5 , 6-dimethoxy-2-nitrobenzyl) oxy] carbonyl} -2,6-dimethylpiperidine and the like. Of these, DNCDP is particularly preferable.
(C) The addition amount of a photobase generator is 2-30 mass parts with respect to 100 mass parts of (A) polyhydroxyamide, Preferably it is 5-25 mass parts, More preferably, it is 10-20 mass parts. Here, when the amount of (C) the photobase generator added is 2 parts by mass or more, the sensitivity and thermosetting are good, and when it is 30 parts by mass or less, the physical properties after thermosetting are good.

(D) Other additives Various compounds can be added to the negative photosensitive resin composition as necessary.
Examples of the surfactant include polypropylene glycol, polyglycols such as polyoxyethylene lauryl ether, and nonionic surfactants composed of derivatives thereof. Fluorosurfactants such as Fluorard (registered trademark) (manufactured by Sumitomo 3M), MegaFac (registered trademark) (manufactured by Dainippon Ink & Chemicals, Inc.), or Lumiflon (registered trademark) (manufactured by Asahi Glass Co., Ltd.) Furthermore, organic siloxane surfactants such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name), DBE (manufactured by Chisso Corporation: trade name), or granol (manufactured by Kyoeisha Chemical Co., Ltd .: trade name) are listed. By adding the surfactant, it is possible to make it more difficult for the non-uniform coating phenomenon of the coating film on the wafer edge during coating to occur.

0-10 mass parts is preferable with respect to 100 mass parts of (A) polyhydroxyamide, and, as for the addition amount in the case of adding surfactant, 0.01-1 mass part is more preferable. If the addition amount is within 10 parts by mass, the heat resistance of the film after thermosetting is good.
Adhesion aids include alkyl imidazolines, butyric acid, alkyl acids, polyhydroxystyrene, polyvinyl methyl ether, t-butyl novolac, epoxy polymers, and silane coupling agents.

Specific preferred examples of the silane coupling agent include 3-methacryloxypropyltrialkoxysilane, 3-methacryloxypropyl dialkoxyalkylsilane, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxy. Reaction of alkylsilane, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane with acid anhydride or acid dianhydride, 3-aminopropyltrialkoxysilane or 3-aminopropyl dialkoxyalkylsilane The thing which converted the amino group into the urethane group and the urea group is mentioned. In this case, the alkyl group includes a methyl group, an ethyl group, a butyl group, the acid anhydride includes maleic anhydride, phthalic anhydride, the acid dianhydride includes pyromellitic dianhydride, 3, 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, etc., urethane group is t-butoxycarbonylamino group, urea group is phenylaminocarbonylamino Group and the like.
The addition amount in the case of adding an adhesion assistant is preferably 0 to 30 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of (A) polyhydroxyamide. If the addition amount is within 30 parts by mass, the heat resistance of the film after thermosetting is good.
Further, a thermal acid generator can be added in order to thermally cure at a lower temperature and convert it into a polybenzoxazole skeleton. As the thermal acid generator, methanesulfonyl chloride, p-toluenesulfonyl chloride and the like are recommended.

(E) Solvent It is preferable to add a solvent to the negative photosensitive resin composition to form a varnish and use it as a solution of the negative photosensitive resin composition. Examples of such a solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, γ-butyrolactone, cyclopentanone, cyclohexanone, isophorone, N, N-dimethyl. Acetamide, dimethyl imidazolinone, tetramethyl urea, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, Ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene Call -3 monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate. These can be used alone or in combination as a solvent. Of these solvents, non-amide solvents are preferred because they have little influence on the photoresist. Specific preferred examples include cyclopentanone, cyclohexanone, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate.
The amount of the solvent added is preferably 100 to 1000 parts by mass with respect to 100 parts by mass of (A) polyhydroxyamide. The addition amount of the solvent is preferably set to a viscosity suitable for the coating apparatus and the coating thickness within the above range, because the production of the cured relief pattern can be facilitated.

<Curing relief pattern and method for manufacturing semiconductor device>
Next, the manufacturing method of a hardening relief pattern is demonstrated concretely below.
(1) The process of forming the photosensitive resin layer which consists of a negative photosensitive resin composition on a board | substrate.
First, the negative photosensitive resin composition solution is applied to a substrate such as a silicon wafer, a ceramic substrate, or an aluminum substrate by spin coating using a spin coater, or a coater such as a die coater or roll coater. . Or it is also possible to apply | coat to a predetermined place using an inkjet nozzle or a dispenser. This is dried at 50 to 140 ° C. using an oven or a hot plate to remove the solvent (hereinafter referred to as “pre-bake”).

(2) A step of exposing with actinic rays through a mask.
Second, the photosensitive resin layer is exposed to active light through a mask. Specifically, exposure with actinic radiation is performed using a contact aligner or a stepper, or light, electron beam, or ion beam is directly irradiated. As the actinic ray, g-line, h-line, i-line, or KrF laser can also be used.
(3) The process heated at 120-190 degreeC.
Third, the entire substrate is heated at 120 to 190 ° C. In this heating step, for example, a hot plate, infrared rays, or electromagnetic induction can be used as a heating means. Among them, it is recommended to heat the pot plate at a temperature of 120 to 190 ° C. for 5 to 180 seconds from the accuracy of controlling the applied temperature and time.

  The heating step is called PEB (Post Exposure Bake), and finally a good pattern can be formed by selecting conditions. In order to obtain a good pattern, it is essential to make a difference in the dissolution rate of the exposed area and the unexposed area in an alkaline aqueous solution. A method for finding the conditions for realizing this will be described. After the photosensitive resin layer is formed on the substrate, for example, on the wafer in accordance with the above-described step (1), scratches reaching the substrate surface are made. Next, a half of the substrate is covered with a light shielding sheet so that a part of the scratch is hidden. Next, the sheet is regarded as a mask, and exposure is performed according to the above-described step (2). Next, PEB is performed for a certain temperature. Next, the light shielding sheet is peeled off, and development is performed in accordance with the process (4) described later until the film in the unexposed area is just removed. The development speed of the unexposed area is obtained from the time required for the development and the film thickness before development measured by a surface level meter across the scratch. Next, the film thickness of the exposed area is measured to determine the speed at which the film thickness of the exposed area decreases. Here, the development speed difference between the exposed area and the unexposed area is obtained, and the condition for increasing the value can be found. A method is recommended in which samples with different exposure amounts, PEB times and temperatures are prepared, and the above-mentioned conditions for increasing the difference in development speed are found.

(4) A step of eluting or removing the unexposed portion with an alkaline aqueous solution.
Fourth, the unexposed portion is eluted or removed with an alkaline aqueous solution. Subsequently, a desired relief pattern is obtained preferably by rinsing with a rinsing liquid. As a developing method, a spray, paddle, dip, or ultrasonic method can be used. As the rinsing liquid, distilled water, deionized water or the like can be used.
The developer used for developing the photosensitive resin layer made of the negative photosensitive resin composition dissolves and removes the alkali-soluble polymer, and needs to be an alkaline aqueous solution in which an alkali compound is dissolved. The alkali compound dissolved in the alkaline aqueous solution may be either an inorganic alkali compound or an organic alkali compound.
Examples of the inorganic alkali compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, disodium hydrogen phosphate, lithium silicate, sodium silicate, potassium silicate. , Lithium carbonate, sodium carbonate, potassium carbonate, lithium borate, sodium borate, potassium borate, and ammonia.

Examples of the organic alkali compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylhydroxyethylammonium hydroxide, methylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, n-propylamine, diethylamine. -N-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine, and triethanolamine.
Furthermore, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol, propanol, or ethylene glycol, a surfactant, a storage stabilizer, and a resin dissolution inhibitor can be added to the alkaline aqueous solution. .

(5) The process of heat-processing the obtained relief pattern.
Fifth, the obtained relief pattern is heat-treated to form a heat-resistant cured relief pattern made of a resin having a polybenzoxazole structure. As the heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, or a pressure oven can be used. As a heating method, a heating method using hot air, infrared rays, or electromagnetic induction is recommended. The temperature is preferably 200 to 450 ° C, more preferably 250 to 400 ° C. The heating time is preferably 15 minutes to 8 hours, and more preferably 1 hour to 4 hours. The atmosphere is preferably in an inert gas such as nitrogen or argon.
A semiconductor device combines a cured relief pattern with a known semiconductor device manufacturing method as a surface protective film, an interlayer insulating film, a rewiring insulating film, a protective film for a flip chip device, or a protective film for a device having a bump structure. Can be manufactured.
The negative photosensitive resin composition of the present invention is also useful for applications such as interlayer insulation of multilayer circuits, cover coating of flexible copper-clad plates, solder resist films, or liquid crystal alignment films.

The present invention will be described based on reference examples and examples.
<Synthesis of polyhydroxyamide>
[Reference Example 1]
To a 100 ml flask was added 8.75 g (33.9 mmol) of 4,4′-oxybisbenzoic acid, 20 ml (274 mmol) of thionyl chloride, 20 ml of methylene chloride, and several drops of dimethylformamide (hereinafter also referred to as “DMF”), and the oil bath temperature. Reflux at 90 ° C. for 3 hours. Thereafter, the pressure was reduced to remove thionyl chloride and methylene chloride to obtain a crude product. The crude product was recrystallized from hexane and dried under reduced pressure to obtain white crystals 4,4′-oxydibenzoyl chloride (hereinafter also referred to as OBBC).

Next, 40 ml of N-methylpyrrolidone (hereinafter also referred to as NMP) is placed in a 100 ml two-necked flask, and 5.494 g (15.0 mmol) of 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane. ) And 1.399 g (33.0 mmol) of LiCl were added at room temperature under a nitrogen atmosphere. After all was dissolved, 4.427 g (15.0 mmol) of OBBC was added while cooling in an ice bath and stirred at room temperature for 24 hours. The polymer solution was dropped into 1 l of water 3: methanol 1 solution, suction filtered, and dried at 40 ° C. under reduced pressure to obtain white solid polyhydroxyamide (P-1). The number average molecular weight measured by gel permeation chromatography (hereinafter also referred to as “GPC”) using tetrahydrofuran (hereinafter also referred to as “THF”) as a developing solution was 5,000, and the weight average molecular weight was 8,000. The GPC used was Jasco co-2065 Plus system, the column was TOSOH TSgel GMR _HR- M, and the flow rate of the developing solution was 1.0 ml / min.

[Reference Example 2]
In a 100 ml two-necked flask, 22.4 g of NMP was put, and 4.18 g (11.4 mmol) of 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane and 1.04 g (24.6 mmol) of anhydrous lithium chloride were added. ) Was added at room temperature under a nitrogen atmosphere and completely dissolved with stirring. Next, 3.30 g (11.2 mmol) of OBBC prepared in the same manner as in Reference Example 1 was added at 0 ° C. over 30 minutes, and the mixture was stirred at room temperature for 24 hours. The polymer solution was added dropwise with stirring to a mixed solution of 1600 ml of water and 200 ml of methanol, and after suction filtration, dried at 40 ° C. under reduced pressure to obtain white solid polyhydroxyamide (P-2). In the infrared absorption spectrum (KBr method, cm ⁻¹ ) of this crystal, characteristic absorptions of OH and C═O were confirmed at 3425 and 1651, respectively. Proton NMR chemical shift (300 MHz, CDCl ₃ solution; ppm) is 10.2 (s, 2H), 9.51 (s, 2H), 8.02, 8.04 (d, 4H), 7.93 (s) 1H), 7.18, 7.20 (d, 4H), 7.00 (s, 4H) and identified as polyhydroxyamide. The yield was 97%.
The number average molecular weight measured by GPC using THF as a developing solution was 9,700, and the weight average molecular weight was 20,800.

<Synthesis of ester compound>
[Reference Example 3]
Put 80 ml of THF in a 200 ml three-necked flask, add 2.48 g (20.8 mmol) of p-cyanophenol and 2.0 g (9.47 mmol) of corkic acid (hexane-1,6-dicarboxylic acid) chloride, and add magnetism. Stir to a homogeneous solution. While maintaining this solution at 0 ° C. under a nitrogen atmosphere, a solution obtained by dissolving 2.88 g (28.4 mmol) of triethylamine in 20 ml of THF was added dropwise over 15 minutes. Thereafter, stirring was continued at room temperature for 20 hours. After separating the precipitated solid, the THF of the obtained solution was distilled off with an evaporator without heating. The obtained liquid was poured into water to obtain a white solid.
Recrystallization was performed with a mixed solution of ethyl acetate and n-hexane at a volume ratio of 3: 5 to obtain 3.31 g of crystals.
The chemical shift of proton NMR (300 MHz, CDCl ₃ solution; ppm) of the crystal was as follows.
7.70, 7.68 (d, 4H) 7.26, 7.24 (d, 4H), 1.74-1.83 (m,: 4H), 1.46-1.51 (m ,: 4H). The ester obtained from this analysis was identified as bis (p-cyanophenyl) corkate. The yield was 93%.

[Reference Example 4]
40 ml of THF was placed in a 200 ml three-necked flask, and 5.92 g (42.6 mmol) of p-nitrophenol and 3.00 g (19.4 mmol) of succinic chloride were added thereto and magnetically stirred to obtain a homogeneous solution.
This solution was cooled to 0 to 3 ° C., and 5.88 g (58.1 mmol) of triethylamine was added dropwise to 30 ml of THF over 15 minutes.
Next, it stirred for 30 minutes, keeping at 0-3 degreeC. Thereafter, stirring was continued at room temperature for 17 hours.
After separating the deposited salt, THF was distilled off with an evaporator, and the obtained paste-like residue was poured into 500 ml of water to obtain an ocherous solid.
Recrystallization with ethyl acetate yielded 5.78 g of granular crystals.
The chemical shift of proton NMR (300 MHz, CDCl ₃ solution; ppm) of the crystal was as follows.
8.29-8.32 (d, 4H) 7.43-7.46 (d, 4H) 3.07 (t,: 4H). In the IR spectrum, a characteristic absorption of carbonyl was observed at 1751 cm ⁻¹ . From this result, this crystal was identified as bis (p-nitrophenyl) succinate. The theoretical values of elemental analysis are C: 53.34, H: 3.36, and N: 7.78, while the measured values are C: 53.62, H: 3.52, and N: 7.52. It was.

[Reference Example 5]
A 200 ml three-necked flask was charged with 80 ml of THF, and 4.35 g (31.3 mmol) of p-nitrophenol and 3.0 g (14.2 mmol) of corkyl chloride were added and magnetically stirred to obtain a homogeneous solution.
While keeping this solution at 0 ° C. under a nitrogen atmosphere, a solution of 4.31 g (42.6 mmol) of triethylamine in 20 ml of THF was added dropwise.
Thereafter, stirring was continued at room temperature for 20 hours, and the precipitated solid was separated.
Then, THF of the obtained solution was distilled off with an evaporator at room temperature.
The obtained liquid was poured into 500 ml of water to obtain a white powder.
Recrystallization was performed with a mixed solution of ethyl acetate and n-hexane at a volume ratio of 1: 4 to obtain 5.80 g of crystals.
The infrared absorption spectrum of the crystal showed absorption at 1751, 1535, 1342, and 864 cm ⁻¹ .
Proton NMR chemical shift (300 MHz, CDCl ₃ solution; ppm) is 8.22-8.27 (d, 4H), 7.29-7.24 (d, 4H), 2.59-2.64 (t, 4H), 1.78-1.83 (m, 4H), 1.48-1.53 (m, 4H) melting point is 114.5 ° C., and the resulting ester is bis (p-nitrophenyl) corkate. It was confirmed. The yield was 98%.

[Example 1]
7 g of polyhydroxyamide (P-1) obtained in Reference Example 1 above, 2 g of p-nitrophenyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 part by weight of DNCDP as a photobase generator were dissolved in 40 g of cyclopentanone, A negative photosensitive resin composition was prepared. DNCDP is an A.D. Mochizuki, T .; Teranishi, and M.M. Synthesized in 75% yield according to Ueda, Macromolecule, 1995, 28, p365. The melting point was 139.2 ° C.
This composition is spin-coated on a 6-inch silicon wafer at 1500 rpm for 10 seconds with a spin coater (MIKASA 1H-D7), and pre-baked on a hot plate at 80 ° C. for 60 seconds to form a coating film having a thickness of 1.1 μm. did. The film thickness was measured with a film thickness measuring device (Dektak 3 system manufactured by Veeco Instruments Inc.).
This coating film was exposed at an exposure amount of 500 mJ / cm ² using a contact exposure machine (mask alignment apparatus M-1S manufactured by Mikasa) having an exposure wavelength of i-line (365 nm) through a reticle with a test pattern. Further, post-exposure baking (PEB) was performed at 160 ° C. for 10 seconds. This was developed using an alkali developer (developer made by AZ Electronic Materials, 2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C. for 60 seconds, rinsed with pure water, and negative. A relief pattern of the mold was formed. An 8 μm line / space pattern was resolved. The film thickness after development was 1.1 μm.

[Example 2]
6 g of polyhydroxyamide (P-2) obtained in Reference Example 2 above, 2.5 g of p-nitrophenyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.5 g of DNCDP as a photobase generator were dissolved in 40 g of cyclopentanone. The solution of the negative photosensitive resin composition was prepared.
The negative photosensitive resin composition solution of the above example was spin-coated on a 6-inch silicon wafer for 10 seconds at 1500 rpm with a spin coater (MIKASA 1H-D7), prebaked at 80 ° C. for 60 seconds with a hot plate, A coating film having a thickness of 1.2 μm was formed.
Using the same contact exposure machine as in Example 1 having an exposure wavelength of i-line (365 nm), this coating film was exposed at an exposure amount of 500 mJ / cm ² and subjected to PEB at 160 ° C. for 10 seconds, under the same conditions as in Example 1. The film was developed for 43 seconds to form a negative relief pattern in which a 6 μm line / space pattern was resolved.

[Example 3]
8 g of polyhydroxyamide (P-2) obtained in Reference Example 2, 0.5 g of bis (p-nitrophenyl) corkate obtained in Reference Example 5 and 1.5 g of DNCDP as a photobase generator It melt | dissolved in 41 g of cyclopentanone, and prepared the solution of the negative photosensitive resin composition. This solution was spin-coated on a silicon wafer at a rotational speed of 5000 ppm for 15 seconds, and then the coating film was scratched and prebaked on an 80 ° C. hot plate for 30 seconds. The film thickness of the coating film was measured to be 1.1 μm from the step at the position of the scratch.
Next, half of the wafer was covered with a black light-shielding film and exposed to 300 mJ / cm ² with i-line ultraviolet rays. The exposed part and the unexposed part of the wafer were each divided into a large number so as to cause scratches, and PEB was performed on a hot plate for 10 seconds in increments of 10 ° C. from 100 ° C. to 180 ° C. Each wafer section obtained here was developed using the 2.38% tetramethylammonium hydroxide aqueous solution of Example 1 at 23 ° C. until the unexposed area was just removed, and the film thickness was measured. Was used to determine the developing speed of the exposed and unexposed film. The result is shown in FIG. Next, PEB was carried out for various times at a temperature of 140 ° C. using a plurality of sections in the same manner. The obtained slice was alkali-developed under the same conditions as above to determine the dissolution rate of the exposed and unexposed areas. The result is shown in FIG.
Next, using this coating film, the exposure time was changed with a stepper and the i-line was irradiated. Thereafter, PEB was carried out at 140 ° C. for 10 seconds, and development was carried out with the same 2.38 mass% tetramethylammonium hydroxide aqueous solution used in Example 1 for 50 seconds.
The film thickness after development at each exposure amount was measured with a step gauge to obtain a relative film thickness based on the film thickness before exposure, and a semi-log plot was made with respect to the exposure amount. The result is shown in FIG.

[Example 4]
8 g of polyhydroxyamide (P-2) obtained in Reference Example 2 above, 0.5 g of bis (p-cyanophenyl) corkate obtained in Reference Example 3 above, and 42 g of DNCDP 1.5 g as a photobase generator A negative photosensitive resin composition was prepared by dissolving in 0.9 g of cyclopentanone. This solution was spin-coated on a silicon wafer at a rotational speed of 5000 ppm for 15 seconds, and then the coating film was scratched and prebaked on an 80 ° C. hot plate for 30 seconds. The film thickness of the coating film was measured to be 1.1 μm from the step at the position of the scratch.
Next, half of the wafer was covered with a black light-shielding film and exposed to 300 mJ / cm ² with i-line ultraviolet rays. PEB was performed on a hot plate at 160 ° C. for 10 seconds. Next, the film was developed at room temperature for 82 seconds using the 2.38% tetramethylammonium hydroxide aqueous solution of Example 1, and the film thickness was measured. The developing speed was 131 Å / sec.

[Example 5]
8 g of polyhydroxyamide (P-2) obtained in Reference Example 2 above, 0.5 g of bis (p-nitrophenyl) succinate obtained in Reference Example 4 above, 1.5 g of DNCDP as a photobase generator Was dissolved in 42.9 g of cyclopentanone to prepare a negative photosensitive resin composition.
This solution was spin-coated on a silicon wafer at a rotation speed of 1500 ppm for 15 seconds, and then the coating film was scratched and prebaked on an 80 ° C. hot plate for 30 seconds. The film thickness of the coating film was measured to be 2.1 μm from the level difference at the scratch.
Next, half of the wafer was covered with a black light-shielding film and exposed to 300 mJ / cm ² with i-line ultraviolet rays. PEB was performed on a hot plate at 150 ° C. for 10 seconds.
Next, the same 2.38 mass% tetramethylammonium hydroxide aqueous solution as that used in Example 1 was used, developed at room temperature for 86 seconds, and the film thickness was measured. Less than a second, the developing speed of the unexposed area was 238 kg / sec.
Further, coating, pre-baking, exposure, PEB, and development were carried out under exactly the same conditions through a mask, and an 8 μm line / space pattern was well resolved.

[Example 6]
The solution prepared in Example 3 was spin coated on a silicon wafer at 3000 rpm for 15 seconds. Pre-baking was performed on a hot plate at 80 ° C. for 30 seconds to obtain a coating film. The thickness of this film was 1.9 μm.
Next, 300 mJ / cm ² exposure was performed with i-line through a mask, and PEB was performed at 140 ° C. for 10 seconds. When development was performed for 50 seconds with the same 2.38 mass% tetramethylammonium hydroxide aqueous solution used in Example 1, the line / space of 8 μm was resolved well.
Next, the wafer on which this pattern was formed was heat-treated at 350 ° C. for 1 hour in a nitrogen atmosphere. When the infrared absorption spectrum of the obtained film was measured, the peak at 1651 cm ⁻¹ derived from the amide of polyhydroxyamide disappeared and the peak at 1049 cm ⁻¹ was generated.
This confirmed that it was converted to a polybenzoxazole film.
[Example 7]
The negative photosensitive resin composition prepared in Example 4 was dropped on a silicon wafer having aluminum sputtered to a thickness of 0.2 μm and a silicon wafer having copper sputtered to a thickness of 1 μm, and applied with a bar coater.
Thereafter, prebaking was performed for 2 minutes on a hot plate at 100 ° C. Using PLA-501F (Canon exposure machine), exposure was performed for 150 seconds with mixed light of g, h, and i lines. The illuminance was 4 mW / cm ² at 350 nm. Thereafter, PEB was performed at 150 ° C. for 10 seconds. The coating film thickness was 3 μm. All the coated surfaces were colorless and mirror-like. This wafer was divided into two and one was heated on a hot plate at 250 ° C. for 1 hour.
These wafers were left in a saturated water vapor atmosphere at 121 ° C. and 2 atm for 24 hours using a PCT (Pressure Cooker Test) apparatus (HAST CHAMBER EHS-221M manufactured by Tabai Espec).
As a result, in the silicon wafer on the copper surface, the part covered with the coating film was slightly yellowed when heated at 250 ° C., but the mirror surface was maintained. As for the aluminum surface, the part covered with the coating film remained colorless and mirror-like in both cases that were not heated at 250 ° C. From this result, it can be seen that the negative photosensitive resin composition prepared in Example 4 has no problem that the underlying metal is corroded.
[Comparative Example 1]
In the negative photosensitive resin composition, a photoacid generator (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene-2- (methylphenyl) acetonitrile) instead of DNCDP (Ciba Specialty Chemicals Co., Ltd.) The same operation as in Example 7 was performed except that CG11397) manufactured by company was used. As a result, although not heated at 250 ° C., the copper surface of the portion covered with the coating film turned brown. In addition, when heated at 250 ° C., the copper surface became dark brown and was not mirror-like. As for the aluminum surface, the part that was not heated at 250 ° C. and the part that was covered with the coating film was not mirror-like.

  The negative photosensitive resin composition of this invention can be used conveniently for manufacture of the polybenzoxazole precursor suitable for using as a protective film of a semiconductor.

The dissolution rate of the film | membrane after performing PEB for 10 second of the negative photosensitive resin composition coating film of Example 3 with respect to the temperature (PEB temperature) of PEB. □ indicates data on a film that was not exposed, and ◆ indicates data on a film that was exposed at 300 mJ / cm ² with i-line. PEB of the negative photosensitive resin composition coating film of Example 3 was carried out at 140 ° C., and the dissolution rate (Dissolution) of the film with respect to the PEB time (PEB time) when developed until the unexposed area was just removed. rate) is plotted. □ indicates data on a film that was not exposed, and ◆ indicates data on a film that was exposed at 300 mJ / cm ² with i-line. The negative photosensitive resin composition coating film of Example 3 was exposed at various exposure amounts, PEB was performed at 140 ° C. for 10 seconds, and the development amount was fixed at 50 seconds, and the remaining amount with respect to the exposure amount (Exposure dose). It is a plot of the film ratio (Normalized film thickness).

Claims (11)

(A) Polyhydroxyamide having a repeating unit represented by the following general formula (I): 100 parts by mass, (B) Ester compound represented by the following general formula (II): 1-50 parts by mass, (C) A negative photosensitive resin composition comprising: a photobase generator: 2 to 30 parts by mass.
Wherein X ₁ is a tetravalent organic group having 2 or more carbon atoms, and X ₂ , Y ₁ and Y ₂ are each independently a divalent organic group having 2 or more carbon atoms. M is an integer of 2 to 200, n is an integer of 0 to 200, and m / (m + n)> 0.5, where m dihydroxydiamide units including X ₁ and Y ₁ And the order of arrangement of n diamide units including X ₂ and Y ₂ is not limited.)

(In the formula, X is a monovalent to tetravalent aliphatic group having 1 to 4 carbon atoms, Z is hydrogen or an electron withdrawing group, p is an integer of 1 to 5, and q is an integer of 1 to 4.)   (B) The negative photosensitive resin composition according to claim 1, wherein Z in the ester compound represented by the general formula (II) is an electron-withdrawing group.   (B) q in the ester compound represented by the said general formula (II) is 2-4, The negative photosensitive resin composition of Claim 1 or 2 characterized by the above-mentioned.   (C) The photobase generator is a compound that generates a secondary amine having at least one substituent at the α-position upon irradiation with actinic rays. The negative photosensitive resin composition as described.   The negative photosensitive resin composition according to claim 4, wherein the secondary amine has a cyclic structure. The negative photosensitive resin composition according to claim 4, wherein the secondary amine is a compound represented by the following general formula (III).
(In formula, R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > may each independently have hydrogen, the C1-C6 alkyl group which may have a substituent, and a substituent. A cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms which may have a substituent, an alkene group having 1 to 6 carbon atoms which may have a substituent, and a substituent. An alkynyl group having 1 to 6 carbon atoms, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent (wherein R ₁ , R ₂ , At least one of R ₃ and R ₄ is not hydrogen), R ₅ and R ₆ are each independently hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a substituent. A C3-C8 cycloalkyl group which may have a C 1-6 alkyl which may have a substituent A xyl group, an optionally substituted alkene group having 1 to 6 carbon atoms, an optionally substituted alkynyl group having 1 to 6 carbon atoms, and an optionally substituted aryl group , A heterocyclic group which may have a substituent, a monocycle which may have a substituent formed by bonding to each other, or a substituent which may be formed by bonding to each other Indicates a polycycle.) (C) A negative photosensitive resin composition according to claim 1, wherein the photobase generator is a compound represented by the following general formula (IV).
(In the formula, R ₇ represents a nitrophenyl group which may have a substituent, and R ₈ and R ₉ each independently represent hydrogen or a C 1-6 which may have a substituent. of an alkyl _group, R 1 to R ₆ are as defined for _R 1 to R ₆ in the general formula (III).) The negative photosensitive resin composition according to claim 7, wherein the compound represented by the general formula (IV) is a compound represented by the following general formula (V).
(In the formula, R ₁₀ has an optionally substituted alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 3 to 8 carbon atoms, and a substituent. An optionally substituted alkoxyl group having 1 to 6 carbon atoms, an alkene group having 1 to 6 carbon atoms which may have a substituent, an alkynyl group having 1 to 6 carbon atoms which may have a substituent, and a substituent An aryl group that may have a substituent, a heterocyclic group that may have a substituent, a monocyclic ring that may have a substituent formed by bonding adjacent R _{10 to} each other, or an adjacent group R ₁₀ represents a polycycle which may have a substituent formed by bonding each other, and R ₈ and R ₉ are each independently hydrogen or a carbon which may have a substituent. 1 represents an alkyl group of 1 to 6 (provided that at least one of R ₈ and R ₉ is hydrogen), and s is 0 -4 represents an integer, and R _{1 to} R ₆ have the same meaning as R _{1 to} R ₆ in the general formula (III). The negative photosensitive resin composition according to claim 7, wherein the compound represented by the general formula (IV) is a compound represented by the following general formula (VI).
(In the formula, R ₈ and R ₉ each independently represent hydrogen or an optionally substituted alkyl group having 1 to 6 carbon atoms (provided that at least one of R ₈ and R ₉ is Are hydrogen), R ₁₁ and R ₁₂ represent an optionally substituted alkoxyl group having 1 to 6 carbon atoms, t represents 0, 1 or 2, and R _{1 to} R ₄ represent the above general formulas. (It has the same meaning as R _{1 to} R ₄ in formula (III).)   (1) The process of forming the photosensitive resin layer which consists of a negative photosensitive resin composition as described in any one of Claims 1-9 on a board | substrate, (2) The process of exposing with actinic light through a mask , (3) a step of heating at 120 to 190 ° C., (4) a step of eluting or removing an unexposed portion with an alkaline aqueous solution, and (5) a step of heat-treating the obtained relief pattern, A method for producing a cured relief pattern.   A semiconductor device having a cured relief pattern obtained by the manufacturing method according to claim 10.