TWI726112B - Photosensitive resin composition and method for manufacturing semiconductor device - Google Patents

Abstract

The present invention provides a photosensitive resin composition that can obtain a cured film having excellent adhesion to metal materials, particularly copper, and high coatability even in heat treatment at low temperatures.

A photosensitive resin composition containing (A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, (B) a photosensitizer, and (C) a liquid under the conditions of 1013 hPa and 25°C and a boiling point of 210°C The above compound is characterized in that, with respect to 100 parts by mass of (A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, 0.1 to 15 parts by mass of the aforementioned (C) is contained at 1013 hPa and 25°C. Liquid and a compound with a boiling point of 210°C or higher.

Description

Photosensitive resin composition and method for manufacturing semiconductor device

The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition suitable for use in surface protective films of semiconductor elements, interlayer insulating films, insulating layers of organic electroluminescent elements, and the like.

唑系樹脂等。在將聚醯亞胺或聚苯并

唑作為表面保護膜或層間絕緣膜使用的情況下，通孔等的形成方法的1種為使用正型光阻的蝕刻。然而，在該方法中，步驟包含光阻的塗布、剝離，而有繁雜這樣的問題存在，於是進行研究一種為使作業步驟合理化而賦予感光性的耐熱性材料。 In the past, surface protection films or interlayer insulating films of semiconductor elements of electronic devices have been widely used for polyimide resins and polybenzos that are excellent in heat resistance and mechanical properties.

Azole resins, etc. In the polyimide or polybenzo

When azole is used as a surface protective film or an interlayer insulating film, one of the formation methods of via holes and the like is etching using a positive photoresist. However, in this method, the steps include coating and peeling of the photoresist, and there is a problem of complexity. Therefore, research is being conducted on a heat-resistant material that imparts photosensitivity in order to rationalize the work steps.

唑係能夠使該等的前驅物的塗膜熱脫水閉環而得到具有優異的耐熱性、機械特性的薄膜。然而，在此情況下，通常需要在350℃左右的高溫下進行加熱處理。但是例如有希望作為新世代記憶體的MRAM(Magnetoresistive Random Access Memory；磁阻式隨機存取記憶體)等不大能承受高溫製成，因此尋 求一種以約250℃以下的低溫的加熱處理將表面保護膜硬化而能得到不比先前以350℃左右的高溫的加熱處理進行硬化的硬化膜遜色的性能之聚醯亞胺系樹脂、聚苯并

唑系樹脂。 Polyimide or polybenzo

The azole series can heat-dehydrate and close the coating film of these precursors to obtain a film having excellent heat resistance and mechanical properties. However, in this case, it is usually necessary to perform heat treatment at a high temperature of about 350°C. However, for example, MRAM (Magnetoresistive Random Access Memory), which is promising as a new-generation memory, is not able to withstand high temperatures. Therefore, it is necessary to seek a low-temperature heat treatment below about 250°C. The protective film is cured to obtain polyimide-based resins and polybenzoic resins that are not inferior to the cured film cured by heat treatment at a high temperature of about 350°C.

Azole resin.

唑系樹脂之方法而言，已知有以下的方法。亦即，閉環促進劑的添加或在單元結構中導入促進低溫下的閉環的有機基之方法，還有使用為賦予鹼溶性而預先閉環的聚醯亞胺或聚苯并

唑之方法等。 The result is a polyimide resin, polybenzoic acid hardened by heat treatment at a low temperature.

As for the azole resin method, the following methods are known. That is, the addition of a ring-closing accelerator or the introduction of an organic group that promotes ring-closure at low temperatures into the unit structure, there is also the use of polyimide or polybenzoic acid, which is ring-closed in advance to impart alkali solubility.

Methods of azole and so on.

In addition, when the heat-resistant resin composition is used for semiconductor applications, the cured film obtained by the heat treatment remains in the device as a permanent film, so the physical properties of the cured film are very important. In order to ensure the reliability of the semiconductor package, the adhesion to the material formed on the surface of the semiconductor wafer is very important. In particular, when used as an insulating film between wiring layers of a wafer-level package, the adhesion to metal materials used for electrodes, wiring, etc. becomes very important.

However, resin compositions containing resins that can be cured by the above-mentioned heat treatment at low temperatures have the problem of low adhesion to metals used as these wiring materials.

It is generally believed that heat-resistant resins have low adhesion strength with metal materials due to their rigid main chain structure. Especially in the case of a cured film of a photosensitive resin composition, the photosensitive and sensitizing agent constituting the resin composition Additives such as chemicals, acid generators, and dissolution regulators will remain in the cured film after heating and hardening, so the adhesion strength will be lower than that of those without additives. The following solutions have been proposed as these solutions: a silane compound consisting of a soluble polymer in an aqueous alkali solution, a photoacid generator, and a silane compound containing 4 or more specific functional groups directly bonded to Al atoms, Ti atoms, and Si atoms Positive photosensitive resin composition (refer to Patent Document 1); or a heat-resistant resin precursor composition composed of a heat-resistant resin precursor such as a polyimide precursor and a specific amine-based compound or thiol derivative ( Refer to Patent Documents 2 to 5).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2008-276190 (pages 1-3)

[Patent Document 2] JP 2007-39486 A (pages 1-3)

[Patent Document 3] Japanese Patent Laid-Open No. 2003-5369 (pages 1-3)

[Patent Document 4] International Publication No. 2014/115233 (pages 1-3)

[Patent Document 5] Japanese Patent Application Laid-Open No. 2015-232688 (pages 1-4)

However, the photosensitive resin composition or heat-resistant resin precursor composition described in Patent Documents 1 to 4 has the problems of poor compatibility with resin and additives and poor coating properties. Therefore, coating is performed on metal wiring with unevenness. , Holes are generated during pre-baking, and the adhesion between the cured film and metal wiring may be reduced. In addition, the resin composition described in Patent Document 5 cannot produce unreacted compounds during polymerization, and may fail to ensure sufficient adhesion when forming a cured film. Therefore, the object of the present invention is to provide a photosensitive resin composition that can obtain a cured film having excellent adhesion to metal materials, especially copper, and high coatability even during heat treatment at low temperatures .

In order to solve the above-mentioned problems, the photosensitive resin composition of the present invention has the following structure. It is a photosensitive resin composition containing (A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, (B) a photosensitizer, and (C) a liquid at 1013 hPa and a boiling point of 25°C The compound of 210°C or higher is characterized by containing 0.1-15 parts by mass of the aforementioned (C) under the conditions of 1013 hPa and 25°C with respect to 100 parts by mass of (A) alkali-soluble resin having an organic group derived from aliphatic diamine The bottom is a liquid compound with a boiling point of 210°C or higher.

The photosensitive resin composition of the present invention has excellent coatability, and even in heat treatment at low temperature, a cured film having excellent adhesion to metal materials, especially copper, can be obtained.

The present invention is a photosensitive resin composition containing (A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, (B) a photosensitizer, and (C) a liquid with a boiling point under the conditions of 1013 hPa and 25°C It is a compound of 210°C or higher, which contains 0.1-15 parts by mass of the aforementioned (C) with respect to 100 parts by mass of (A) alkali-soluble resin having an organic group derived from aliphatic diamine under the conditions of 1013 hPa and 25°C A compound that is liquid and has a boiling point of 210°C or higher. Hereinafter, component (A), component (B), and (C) compound may be omitted, respectively.

The reasons why the cured film of the photosensitive resin composition of the present invention hardened by heat treatment has excellent adhesion to metals, especially copper, include the following points. That is, it contains 0.1-15 parts by mass of the (C) compound relative to 100 parts by mass of the (A) component, and by further increasing the boiling point, the residual amount of the (C) compound in the cured film can be minimized The point; the (C) compound remaining in the cured film can be restricted to the point where it is difficult to evaporate and the boundary part of the copper substrate. Thereby, the part close to the copper substrate interface of the cured film is locally swollen and softened. Therefore, the cured film can penetrate into the fine irregularities of the copper substrate, and the adhesion with the copper substrate can be improved by the anchoring effect. Furthermore, it has a structure with an amide group, and the nitrogen atom is coordinated with copper, so whether it is physically or chemically, the adhesion between the cured film and copper can be improved. Furthermore, the photosensitive resin composition contains (D) a compound represented by the general formula (5) and (E) a compound represented by the general formula (6), so that the adhesion to copper can be further improved.

(In the general formula (5), R ⁷ to R ⁹ represent any one of an oxygen atom, a sulfur atom, or a nitrogen atom ^{, at least one of R 7} to R ⁹ represents a sulfur atom, and l represents 0 or 1. When l is 0, R ⁷ represents an oxygen atom or a sulfur atom; when l is 1, R ⁷ represents a nitrogen atom. m and n represent 1 or 2, and R ¹⁰ to R ¹² represent each independently A hydrogen atom or an organic group with 1 to 20 carbon atoms.)

(In the general formula (6), R ¹³ represents a hydrogen atom or an alkylene group having 1 or more carbon atoms, R ¹⁴ represents an alkylene group having 2 or more carbon atoms, and R ¹⁵ represents an alkylene group having at least 2 carbon atoms. , Oxygen atom, and nitrogen atom any one of 1-4 valence organic groups, k represents an integer of 1-4.)

Therefore, the photosensitive resin composition of the present invention can obtain a cured film with high adhesion to metal materials, especially copper, even in heat treatment at a low temperature of 250°C or less.

In addition, the photosensitive resin composition of the present invention has excellent coatability. The coating property was judged to be excellent when the photosensitive resin composition was coated on a metal wiring having unevenness and prebaked, and no holes were formed at the interface or vertical streaks were not formed on the surface of the coating film. The reason why the photosensitive resin composition of the present invention has excellent coating properties is considered to be that the (C) compound has a high boiling point and therefore reduces the rapid volatilization of the solvent during coating, and can suppress holes or vertical streaks in the prebaked film.

唑、聚醯胺醯亞胺、及該等的前驅物樹脂中之1種以上的樹脂為佳。 (A) Alkali-soluble resins having organic groups derived from aliphatic diamines used in the present invention contain polyimine, polybenzo

One or more resins among azoles, polyamide imines, and these precursor resins are preferable.

As for the polyimide precursor preferably used in the present invention, polyimide, polyimide, polyimide, polyisoimide, etc. can be cited. For example, polyamide acids can react tetracarboxylic acids, corresponding tetracarboxylic dianhydrides, tetracarboxylic acid diesters, etc., with diamines, corresponding diisocyanate compounds, and trimethylsilylated diamines. get. The polyimide system can be obtained by, for example, dehydrating and ring-closing the polyimide obtained by the aforementioned method by heating or chemical treatment such as acid or alkali.

唑前驅物而言，可列舉：聚羥基醯胺。例如，聚羥基醯胺係能夠使雙胺基苯酚與二羧酸、對應的二羧醯氯、二羧酸活性酯等反應而得到。聚苯并

唑係例如能夠藉由將由前述方法得到的聚羥基醯胺以加熱、或是磷酸酐、鹼、碳二醯亞胺化合物等化學處理進行脫水閉環而得到。 Is preferably used in the polybenzo

Examples of the azole precursor include polyhydroxyamide. For example, the polyhydroxyamide system can be obtained by reacting diaminophenol with dicarboxylic acid, corresponding dicarboxylic acid chloride, dicarboxylic acid active ester, and the like. Polybenzo

The azole series can be obtained by, for example, dehydrating and ring-closing the polyhydroxyamide obtained by the aforementioned method with heating, or chemical treatment such as phosphoric anhydride, alkali, or carbodiimide compound.

The polyamide imine precursor system preferably used in the present invention can be obtained by reacting, for example, tricarboxylic acid, corresponding tricarboxylic acid anhydride, halogenated tricarboxylic acid anhydride, and the like with diamine or diisocyanate. The polyimide imine system can be obtained, for example, by subjecting the precursor obtained by the aforementioned method to heating or chemical treatment such as acid or alkali to perform dehydration and ring closure.

The (A) alkali-soluble resin system having an organic group derived from an aliphatic diamine used in the present invention preferably has one or more types selected from structural units represented by the following general formulas (7) to (10). It may be composed of two or more kinds of resins having these structural units, or may be a resin obtained by copolymerizing two or more kinds of structural units.

(In the general formulas (7) to (10), R ¹⁶ and R ¹⁹ represent a tetravalent organic group, R ¹⁷ , R ¹⁸ and R ²¹ represent a divalent organic group, and R ²⁰ represents a trivalent organic group. R ²² represents an organic group with 2 to 4 valences, and R ²³ represents an organic group with 2 to 12 valences. Preferably, R ¹⁶ to R ²³ have aromatic and/or aliphatic rings. R ²⁴ represents hydrogen. A monovalent hydrocarbon group with 1 to 20 atoms or carbon atoms. p represents an integer from 0 to 2, and q represents an integer from 0 to 10.)

In the general formulae (7) to (10), R ¹⁶ represents a residue of a tetracarboxylic acid derivative, R ¹⁸ represents a residue of a dicarboxylic acid derivative, R ²⁰ represents a residue of a tricarboxylic acid derivative, and R ²² represents a residue of a tricarboxylic acid derivative. Represents the residue of a di-, tri- or tetra-carboxylic acid derivative. The acid components constituting R ¹⁶ , R ¹⁸ , R ²⁰ , and R ²² (COOR ²⁴ )p include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, and bis(carboxyphenyl) Hexafluoropropane, biphthalic acid, diphenyl ketone dicarboxylic acid, triphenyl dicarboxylic acid, etc. are examples of dicarboxylic acids; 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, two Phenyl ether tricarboxylic acid and biphenyl tricarboxylic acid are examples of tricarboxylic acids; 1,2,4,5-benzenetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-Biphenyltetracarboxylic acid, 2,2',3,3'-Biphenyltetracarboxylic acid, 3,3',4,4'-Diphenylketonetetracarboxylic acid, 2,2',3,3' -Diphenylketone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1- Bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3 -Dicarboxyphenyl) methane, bis(3,4-dicarboxyphenyl) bis(3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3, Aromatic tetracarboxylic acids such as 6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, or butanetetracarboxylic acid, 1,2,3, Aliphatic tetracarboxylic acids such as 4-cyclopentanetetracarboxylic acid and the like are examples of tetracarboxylic acids. Among them, in the general formula (10), one or two carboxyl groups of each of the tricarboxylic acid and the tetracarboxylic acid correspond to the COOR ²⁴ group. These acid components can be used directly or as acid anhydrides, active esters, and the like. Moreover, these two or more acid components can also be used in combination.

In the general formulas (7) to (10), R ¹⁷ , R ¹⁹ , R ²¹ and R ²³ represent diamine derivative residues. Examples of diamine components constituting R ¹⁷ , R ¹⁹ , R ²¹ , and R ²³ (OH)q include bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3- Amino-4-hydroxyphenyl), bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methane (bis(3-amino-4-hydroxylbenzyl) )methylene), bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, and bis(3-amino-4-hydroxyphenyl)pyridium containing hydroxyl Diamines; 3-sulfonic acid-4,4'-diaminodiphenyl ether and other sulfonic acid-containing diamines; dimercaptophenylenediamine and other thiol group-containing diamines; 3,4'-diamine Diphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'- Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1 ,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4 -Aminophenoxyphenyl), bis(3-aminophenoxyphenyl), bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy) )Phenyl)ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl -4,4'-Diaminobiphenyl, 3,3'-Dimethyl-4,4'-Diaminobiphenyl, 3,3'-Diethyl-4,4'-Diaminobiphenyl Benzene, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl Aromatic diamines such as benzene, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, or some of the hydrogen atoms of these aromatic rings have carbon number 1~ 10 alkyl or fluoroalkyl, halogen atom and other substituted compounds; cyclohexanediamine, methylene bicyclohexylamine and other alicyclic diamines, etc. These diamines can be used directly or as corresponding diisocyanate compounds and trimethylsilylated diamines. Moreover, these two or more types of diamine components can also be used in combination. For applications requiring heat resistance, it is preferable to use aromatic diamines of 50 mol% or more of the entire diamine.

^{The R 16} to R ²³ systems of the general formulae (7) to (10) can contain phenolic hydroxyl groups, sulfonic acid groups, thiol groups, etc. in their skeletons. By using a resin having a phenolic hydroxyl group, a sulfonic acid group, or a thiol group, it becomes a photosensitive resin composition having alkali solubility.

Moreover, it is preferable to have a fluorine atom in the structural unit of (A) component. Permeation of fluorine atoms can impart hydrophobicity to the surface of the film during alkali development, and can suppress permeation from the surface. In order to fully obtain the anti-permeation effect of the interface, the content of fluorine atoms in 100% by mass of the component (A) is preferably 10% by mass or more, and from the viewpoint of solubility in an aqueous alkali solution, it is preferably 20% by mass. %the following.

The (A) alkali-soluble resin system having an organic group derived from aliphatic diamine used in the present invention preferably has R ¹⁷ , R ²¹ , and R ²³ having the aforementioned organic group derived from aliphatic diamine. The aforementioned organic group derived from aliphatic diamine can be obtained by copolymerizing (a) aliphatic diamine.

From the viewpoint of improving the adhesion between the cured film and the metal, the content of the aforementioned aliphatic diamine-derived organic group is preferably 1 mol% or more of the entire diamine, and more preferably 3 mol% or more. On the other hand, from the viewpoint of improving heat resistance, it is preferably 50 mol% or less, and more preferably 40 mol% or less.

Regarding the aforementioned (a) aliphatic diamine, the following compounds can be cited. Also include: ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane , 2-Methyl-1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- Diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-cyclohexanediamine, 1,3 -Cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis (Aminomethyl) cyclohexane, 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(2-methylcyclohexylamine), bis(3-amino) Propyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylheptasiloxane, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176 , D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP -2009, RT-1000, HE-1000, HT-1100, HT-1700, (the above are trade names, HUNTSMAN (stock) system), etc. These compounds may also contain -S-, -SO-, -SO ₂ -, -NH-, -NCH ₃ -, -N(CH ₂ CH ₃ )-, -N(CH ₂ CH ₂ CH ₃ )- , -N(CH(CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, -NHCONH-, etc. bonding.

In addition, in order to improve the storage stability of the photosensitive resin composition of the present invention, component (A) is a blocking agent using monoamine, acid anhydride, monocarboxylic acid, monocarboxylic acid chloride compound, monoactive ester compound, etc. It is better to seal the end of the main chain.

The introduction ratio of the monoamine used as the blocking agent is preferably 0.1 mol% or more, and particularly preferably 5 mol% or more with respect to all amine components. On the other hand, it is preferably 60 mol% or less, and particularly preferably 50 mol% or less.

The introduction ratio of the acid anhydride, monocarboxylic acid, monocarboxylic acid chloride compound, or monoactive ester compound used as the blocking agent is preferably 0.1 mol% or more, particularly preferably 5 mol% relative to the diamine component Above, it is preferably 100 mol% or less, particularly preferably 90 mol% or less. It is also possible to introduce a plurality of different terminal groups by reacting a plurality of capping agents.

In terms of monoamines, aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5- Aminosalic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2 -Aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these compounds can be used.

In terms of acid anhydrides, monocarboxylic acids, monocarboxylic acid chloride compounds, and monoactive ester compounds, phthalic anhydride, maleic anhydride, nadic acid anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxy ortho Acid anhydrides such as phthalic anhydride; 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1 -Hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. Carboxylic acids and monocarboxylic acid chloride compounds derived from the chlorination of these carboxyl groups; by terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene , 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and other dicarboxylic acids, which are monocarboxylic acid chloride compounds and monocarboxylic acid chlorides derived from the chlorination of only one of the carboxyl groups The active ester compound obtained by the reaction of the compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyimide, etc. Two or more of these compounds can be used.

In addition, the blocking agent system introduced into the component (A) can be easily detected by the following method. For example, dissolving the resin into which the blocking agent is introduced in an acidic solution is decomposed into the amine component and the acid anhydride component as constituent units, and can be easily detected by gas chromatography (GC) or nuclear magnetic resonance (NMR) measurement. The end-capping agent used in the present invention. It can also be easily detected by directly using thermal decomposition gas chromatography (PGC) or infrared spectroscopy and ¹³ C-NMR spectroscopy to measure the resin component with the capping agent introduced.

In the component (A) used in the present invention, it is preferable that the repeating number of the unit structure having at least one selected from the structural units represented by the general formulas (7) to (10) is in the range of 3 to 1000. If the number of repetitions of the aforementioned structural unit is 3 or more, a thick film can be easily formed, which is preferable; if it is 1,000 or less, the photosensitive characteristics of the photosensitive resin composition can be maintained, which is preferable.

In addition, the component (A) in the present invention may be composed of only one or more structural units selected from the structural units represented by the general formulas (7) to (10), or may be a copolymerization with other structural units Things or mixtures.

From the viewpoint of improving the heat resistance of the cured film obtained, it contains at least 10% by mass of the total component (A) selected from the structural units represented by the general formulas (7) to (10) The above structural unit is preferably, more preferably 30% by mass or more, and most preferably 100% by mass.

In the case of copolymerization or mixing with other structural units, the type and amount of structural units used in the copolymerization or mixing are selected within the range of not impairing the mechanical properties of the film obtained by the final heat treatment Better. The main chain skeleton of the other structural unit includes, for example, benzimidazole, benzothiazole, and the like.

The photosensitive resin composition of the present invention contains (B) a photosensitizer, and the (B) photosensitizer may be a negative type that is cured by light or a positive type that can be dissolved by light. The former is preferably (b-1) a photopolymerization initiator and a polymerizable unsaturated compound, and the latter is preferably a (b-2) quinonediazide compound.

唑、2-巰基苯并咪唑等巰基類；N-苯基甘胺酸、N-甲基-N-苯基甘胺酸、N-乙基-N-(對氯苯基)甘胺酸、N-(4-氰基苯基)甘胺酸等甘胺酸類；1-苯基-1,2-丁二酮-2-(o-甲氧基羰基)肟、1-苯基-1,2-丙二酮-2-(o(乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(o-乙氧基羰基)肟、1-苯基-1,2-丙二酮-2-(o-苯甲醯基)肟、雙(α-異亞硝基苯丙酮肟)間苯二甲醯基 (bis(α-isonitrosopropiophenone oxime)isophthal)、1,2-辛二酮-1-[4-(苯硫基)苯基]-2-(o-苯甲醯基肟)、OXE02(商品名、Ciba Specialty Chemicals(股)製)、NCI-831(商品名、ADEKA股份有限公司製)等肟類；2-苄基-2-二甲基胺基-1-(4-

啉基苯基)-丁烷-1-2-甲基-1[4-(甲硫基)苯基]-2-

啉基丙-1-酮等α-胺基烷基苯酮類；2,2’-雙(o-氯苯基)-4,4’,5,5’-四苯基聯咪唑等。 The photopolymerization initiator in (b-1) includes, for example, benzophenone, Michelone, 4,4,-bis(diethylamino)benzophenone, 3, Diphenyl ketones such as 3,4,4,-tetra (peroxy tertiary butyl carbonyl) benzophenone; 3,5-bis (diethylamino benzylidene)-N-methyl-4 -Piperidone, 3,5-bis(diethylaminobenzylidene)-N-ethyl-4-piperidone and other benzylidene compounds; 7-diethylamino-3-nonyl incense Bean, 4,6-dimethyl-3-ethylaminocoumarin, 3,3-carbonylbis(7-diethylaminocoumarin), 7-diethylamino-3- (1-methylbenzimidazolyl) coumarin, 3-(2-benzothiazolyl)-7-diethylamino coumarin and other coumarins; 2-tertiary butyl anthraquinone, Anthraquinones such as 2-ethylanthraquinone and 1,2-benzoanthraquinone; Benzoins such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; ethylene glycol bis(3-mercaptopropionate) ), 2-mercaptobenzothiazole, 2-mercaptobenzo

Thiol, 2-mercaptobenzimidazole and other mercapto groups; N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-(p-chlorophenyl)glycine, Glycine such as N-(4-cyanophenyl)glycine; 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1, 2-propanedione-2-(o(ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1, 2-propanedione-2-(o-benzyl) oxime, bis(α-isonitrosopropiophenone oxime) isophthal), 1,2 -Octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzyloxime), OXE02 (trade name, manufactured by Ciba Specialty Chemicals), NCI-831 (commodity) Name, manufactured by ADEKA Co., Ltd.) and other oximes; 2-benzyl-2-dimethylamino-1-(4-

(Alkolinylphenyl)-butane-1-2-methyl-1[4-(methylthio)phenyl]-2-

Alpha-amino alkyl phenones such as hydroxyprop-1-one; 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, etc.

Among these, the above-mentioned oximes are preferred, and 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2- Propanedione-2-(o-benzyl) oxime, bis(α-isonitrosopropiophenone oxime) isophthalic acid, 1,2-octanedione-1-[4-(benzene Thio)phenyl]-2-(o-benzyl oxime), OXE02, NCI-831. These systems can be used alone or in combination of two or more types.

Among these, from the viewpoint of photoreaction, suitable ones are selected from the above-mentioned benzophenones, glycines, sulfhydryls, oximes, α-aminoalkylphenones, 2,2' -A combination of bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

The content of the photopolymerization initiator in (b-1) is preferably 0.1 to 60 parts by mass, and more preferably 0.2 to 40 parts by mass relative to 100 parts by mass of the total amount of the component (A). If it is 0.1 parts by mass or more, it is preferable to generate sufficient free radicals by light irradiation and increase sensitivity. If it is 60 parts by mass or less, excessive free radicals are generated and light is not irradiated. Hardens and enhances alkali developability.

The polymerizable unsaturated compound in (b-1) includes, for example, unsaturated double bond functional groups such as vinyl, allyl, methacrylic, and methacrylic groups and/or propargyl groups Among these, from the viewpoint of polymerizability, a conjugated vinyl group, a methacryloyl group, or a methacryloyl group is preferable as an unsaturated triple-bonded functional group such as a group.

In addition, from the viewpoint of stability, the number of functional groups contained is preferably 1 to 4, and each functional group may not be the same group.

The number average molecular weight of the polymerizable unsaturated compound in (b-1) is not particularly limited, but from the viewpoint of good compatibility with the polymer and the reactive diluent, the number average molecular weight is preferably 800 or less. In addition, for the purpose of suppressing the solubility to the developer after exposure, the number average molecular weight is preferably 30 or more.

Specific examples of the polymerizable unsaturated compound in (b-1) include: diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and diethylene glycol Dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane two Methacrylate, trimethylolpropane trimethacrylate, styrene, α-methylstyrene, 1,2-dihydronaphthalene, 1,3-diisopropenylbenzene, 3-methylstyrene , 4-methylstyrene, 2-vinylnaphthalene, butyl acrylate, butyl methacrylate, isobutyl acrylate, hexyl acrylate, isooctyl acrylate, isobornyl acrylate, isobornyl methacrylate, methyl methacrylate Cyclohexyl acrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1 ,4-Butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1 , 10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, neopentylerythritol triacrylate, neopentaerythritol tetraacrylate, neopentaerythritol trimethacrylate , Neopentyl erythritol tetramethacrylate, dineopentaerythritol hexaacrylate, dineopentaerythritol hexamethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1 , 3-Dipropenyloxy-2-hydroxypropane, 1,3-dimethylpropenyloxy-2-hydroxypropane, methylene bisacrylamide, N,N-dimethylacrylamide, N-Hydroxymethacrylamide, 2,2,6,6-tetramethylpiperidine methacrylate, 2,2,6,6-tetramethylpiperidine acrylate, -N methacrylate -Methyl-2,2,6,6-tetramethylpiperidine, acrylic acid-N-methyl-2,2,6,6-tetramethylpiperidine, ethylene oxide modified double Phenol A diacrylate, bisphenol A dimethacrylate modified with ethylene oxide, N-vinylpyrrolidone, N-vinylcaprolactam, etc. These can be used alone or in combination of two or more kinds.

Among these, particularly preferred ones include 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, Isobornyl acrylate, isobornyl methacrylate, neopentyl erythritol triacrylate, neopentyl erythritol tetraacrylate, neopentyl erythritol trimethacrylate, neopentyl erythritol tetramethacrylate, two new Pentyleneerythritol hexaacrylate, dineopentaerythritol hexamethacrylate, methylene bisacrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, methacrylic acid- 2,2,6,6-Tetramethylpiperidine, acrylate-2,2,6,6-tetramethylpiperidine, methacrylate-N-methyl-2,2,6,6-tetra Methyl piperidine ester, -N-methyl-2,2,6,6-tetramethyl piperidine acrylate, bisphenol A diacrylate modified with ethylene oxide, modified with ethylene oxide The bisphenol A dimethacrylate, N-vinylpyrrolidone, N-vinylcaprolactam and so on.

The content of the polymerizable unsaturated compound in (b-1) is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the component (A). For the purpose of suppressing the solubility to the developer after exposure, it is more preferably 3 parts by mass or more, and for the purpose of obtaining a pattern shape with high verticality, it is more preferably 20 parts by mass or less.

The quinone diazide compound of (b-2) includes ester-bonded sulfonic acid of quinone diazide and polyhydroxy compound, and sulfonic acid of quinone diazide and polyamine group. Compounds are formed by sulfamide bonding, quinonediazide sulfonic acid and polyhydroxy polyamine compounds are formed by ester bonding and/or sulfamide bonding, and the like. All functional groups of these polyhydroxy compounds, polyamine compounds, and polyhydroxy polyamine compounds may not be substituted with quinone diazide, but the average back functional group is 40 mol% or more as quinone diazide It is better to replace. By using such a quinonediazide compound, it is possible to obtain a positive-type photosensitive resin composition that is sensitive to the i-line (wavelength of 365 nm), h-line (wavelength of 405 nm), and g-line (wavelength of 436 nm) of mercury lamps that are general ultraviolet rays.

Examples of polyhydroxy compounds include: Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ , BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylene Tris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML- PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML- HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (the above are trade names, manufactured by Honshu Chemical Industry), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP , BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (the above are the trade names, manufactured by Asahi Organic Materials Industry), 2,6 -Dimethoxymethyl-4-tertiary butylphenol, 2,6-dimethoxymethyl p-cresol, 2,6-diethoxymethyl p-cresol, naphthol, tetrahydroxy Diphenyl ketone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry), novolak resin, etc., but not limited to these.

Polyamine-based compound systems include: 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, etc., but not limited to these.

In addition, examples of the polyhydroxypolyamine compound system include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-dihydroxybenzidine, etc., but are not limited to these.

Among them, the (b-2) quinonediazide compound is preferably an ester containing a phenol compound and 5-naphthoquinonediazidesulfonyl or 4-naphthoquinonediazidesulfonyl, whereby High sensitivity and higher resolution can be obtained by i-line exposure.

In order to improve the contrast of the pattern, the content of the (b-2) quinonediazide compound relative to 100 parts by mass of the (A) component is preferably 20 parts by mass or more, and more preferably 40 parts by mass or more. In addition, in order to increase the sensitivity and reduce the necessary exposure amount, it is preferably 200 parts by mass or less, and more preferably 150 parts by mass or less. Sensitizers and the like can be further added as needed.

The photosensitive resin composition of the present invention contains (C) a compound that is liquid under conditions of 1013 hPa and 25°C and has a boiling point of 210°C or higher. By containing 0.1-15 parts by mass of the aforementioned (C) compound with respect to 100 parts by mass of the (A) component to further increase the boiling point, the residual amount of the (C) compound can be minimized when the cured film is formed . The concentration of the remaining (C) compound at the boundary between the copper substrate and the copper substrate, which is difficult to evaporate, will increase in concentration. As a result, the cured film near the copper substrate interface is locally swollen, and the cured film is softened. Therefore, the cured film can penetrate into the fine irregularities of the copper substrate, and the adhesion with the copper substrate can be improved by the anchoring effect. Furthermore, when curing the photosensitive resin composition of the present invention, the total content of the (C) compound in the cured film relative to the total mass of the cured film is preferably 0.005% by mass or more, more preferably 0.05% by mass Above, it is preferably 5% by mass or less, and more preferably 3% by mass or less. By making the total content of the (C) compound above 0.005 mass%, the adhesion to the copper substrate will be improved; by below 3 mass%, the compound itself will outgas, which can not impair reliability .

In addition, as the reason for the excellent coating property, the compound (C) has a high boiling point and therefore suppresses rapid volatilization during coating, thereby allowing coating to be carried out even on metal wiring with unevenness. Hole.

From the viewpoint of making it easy to remain in the film after the heat treatment, the compound (C) preferably has a boiling point of 210°C or higher. In addition, from the viewpoint of the processing time of the prebaking and the developability of the prebaked film, the boiling point is preferably 400°C or less. When the boiling point cannot be measured under normal pressure, it can be found in the General Catalogue 2008-2009 (No. 39) p. 2173 of Tokyo Chemical Industry Co., Ltd. (Source: Sceience and Petroleum, Vol. II. p. 1281 (1938) ) Boiling point conversion table, converted to boiling point under normal pressure.

The mass% of the compound (C) in the cured film is measured by the purge and trap method or the TPD-MS method on the collected cured film, by measuring the mass of the compound from the alkali-soluble resin (a) The specific gravity of the components calculates this value, and the mass% of the compound in the cured film can be calculated.

Specific examples of the compound (C) include: 1,3-dimethyl-2-imidazolidinone (boiling point 220°C), N,N-dimethylpropyleneurea (N,N-dimethylpropyleneurea) ( (Boiling point 246℃), 3-methoxy-N,N-dimethylpropanamide (boiling point 216℃), 3-butoxy-N,N-dimethylpropanamide (boiling point: 252℃), δ-valerolactone (boiling point 230°C), 2-phenoxyethanol (boiling point: 245°C), 2-pyrrolidone (boiling point: 245°C), 2-methyl-1,3-propanediol (boiling point: 213 ℃), diethylene glycol butyl ether (boiling point: 230℃), triacetin (boiling point: 260℃), butyl benzoate (boiling point 250℃), cyclohexylbenzene (236℃), bicyclohexane (239℃), o-nitroanisole (273℃), diethylene glycol monobutyl ether (230℃), triethylene glycol monomethyl ether (248℃), 3-methoxy-N , N-Dimethylpropanamide (boiling point: 216°C), N-cyclohexyl-2-pyrrolidone (boiling point: 154°C/7mmHg, normal pressure boiling point conversion: 305°C), N-(2-hydroxyl Ethyl)-2-pyrrolidone (boiling point: 175°C/10mmHg, when converted to boiling point at normal pressure: 313°C) and the like. Among these, from the viewpoint of adhesion to copper, the (C) compound preferably has a structure represented by the following general formulas (1) to (4).

(In the general formulas (1)~(4), R ¹ represents hydrogen or an alkyl group with 1 to 5 carbons, R ² represents a divalent organic group with 1 to 5 carbons, and R ⁵ represents hydrogen or a carbon number. The organic group of 1 to 5, R ³ , R ⁴ and R ⁶ each independently represent an organic group of 1 to 5 carbon atoms, and n represents an integer in the range of 1 to 3.)

In addition, the (C) compound system may contain two or more types, and may also be used as a polymerization solvent for the (A) component.

In the case of the polymerization solvent of the component (A), after completion of the polymerization reaction, it is possible to include a specific amount in the photosensitive resin composition of the present invention by reprecipitation in a poor solvent such as pure water, washing, purification, and drying.

The content of the (C) compound relative to 100 parts by mass of the (A) resin is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. By setting it to 0.1 parts by mass or more, the adhesion to copper can be improved, and by setting it to 15 parts by mass or less, it is possible to form a desired patterned film when forming a developing film.

The photosensitive resin composition of the present invention preferably contains (D) a compound represented by the general formula (5) (hereinafter sometimes abbreviated as the (D) component). By containing the component (D), the adhesion between the film and the metal material, especially copper, after heat curing is significantly improved. This is because the sulfur atom or nitrogen atom of the compound represented by the general formula (5) effectively interacts with the metal surface, and also because of the relationship of the three-dimensional structure that easily interacts with the metal surface. Due to these effects, the photosensitive resin composition of the present invention can obtain a cured film excellent in adhesion to metal materials. In particular, the compound that interacts with copper, by containing the compound, the adhesion between the film and the metal material after heat hardening is greatly improved.

(In the general formula (5), R ⁷ to R ⁹ represent any of an oxygen atom, a sulfur atom, or a nitrogen atom, ^{and at least one of R 7} to R ⁹ represents a sulfur atom. 1 represents 0 or 1. When l is 0, R ⁷ represents an oxygen atom or a sulfur atom; when l is 1, R ⁷ represents a nitrogen atom. m and n represent 1 or 2. ^{R 10} to R ¹² represent each independently A hydrogen atom or an organic group with 1 to 20 carbon atoms. ^{Examples of R 10} to R ¹² include hydrogen atom, alkyl group, cycloalkyl group, alkoxy group, alkyl ether group, alkyl silyl group, and alkoxy group. A silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, a combination thereof, etc., may further have a substituent.)

The following compounds can be cited as examples of compounds represented by the general formula (5), but they are not limited to the following structures.

((D) The content of the compound represented by the general formula (5) is preferably 1-40 parts by mass relative to 100 parts by mass of the component (A), for the purpose of suppressing the solubility to the developer after exposure From a standpoint, it is more preferably 3 parts by mass or more, and from the viewpoint of storage stability, it is more preferably 20 parts by mass or less.

The photosensitive resin composition of the present invention preferably contains (E) a compound represented by the following general formula (6) (hereinafter sometimes abbreviated as the (E) component). By containing the component (E), it is possible to suppress the decrease in the mechanical properties of the cured film after the reliability evaluation and the adhesion with the metal material.

(In the general formula (6), R ¹³ represents a hydrogen atom or an alkylene group having 1 or more carbon atoms, R ¹⁴ represents an alkylene group having 2 or more carbon atoms, and R ¹⁵ represents an alkylene group having at least 2 carbon atoms. , Oxygen atom, and nitrogen atom any one of 1-4 valence organic groups, k represents an integer of 1-4.)

The component (E) is used as an antioxidant to suppress the oxidative deterioration of the aliphatic group or phenolic hydroxyl group of the component (A). In addition, the rust-preventing effect on the metal material can inhibit the oxidation of the metal material.

In addition, when the cured film is formed, the adhesion between the cured film and the metal material can be improved through the interaction with the (A) component in the cured film and the metal material. In order to more efficiently interact with both the (A) component in the cured film and the metal material, k is more preferably an integer of 2 to 4. As for R ¹⁵ , examples include: alkyl, cycloalkyl, aryl, aryl ether, carboxy, carbonyl, allyl, vinyl, heterocyclic, -O-, -NH-, -NHNH- , And a combination of these, etc., may further have a substituent. Among them, from the point of view of the solubility to the developer solution and the metal adhesion, it is preferable to contain alkyl ether and -NH-. From the interaction with the component (A) and the formation of metal complexes From the point of view of the resulting metal adhesion, -NH- is more preferable.

Moreover, the addition amount of (E) component is 0.1-10 mass parts with respect to 100 mass parts of (A) components, More preferably, it is 0.5-5 mass parts. The addition amount of 0.1 parts by mass or more can suppress the oxidative degradation of aliphatic groups or phenolic hydroxyl groups, and the rust-preventing effect on the metal material can suppress the oxidation of the metal material, which is preferable. In addition, by making the addition amount 10 parts by mass or less, it is possible to suppress the decrease in the sensitivity of the positive photosensitive resin composition before curing through the interaction with the photosensitive agent, which is preferable.

(E) The component system includes the following compounds as examples, but is not limited to the following structure.

烷、丙二醇單甲基醚、丙二醇單乙基醚等醚類、丙酮、甲基乙基酮、二異丁基酮等酮類、醋酸乙酯、醋酸丁酯、醋酸異丁酯、醋酸丙酯、丙二醇單甲基醚乙酸酯、乙酸-3-甲基-3-甲氧基丁酯等酯類、乳酸乙酯、乳酸甲酯、二丙酮醇、3-甲基-3-甲氧基丁醇等醇類、甲苯、二甲苯等 芳香族烴類等。可含有2種以上的此等溶劑。 The photosensitive resin composition of the present invention may optionally contain a solvent. Preferred examples of solvents include: N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide , Dimethyl sulfoxide and other polar aprotic solvents, tetrahydrofuran, two

Ethers such as alkane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate , Propylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate and other esters, ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxy Alcohols such as butanol, aromatic hydrocarbons such as toluene and xylene, etc. It may contain two or more of these solvents.

The content of the solvent is preferably 70 parts by mass or more, more preferably 100 parts by mass or more, from the viewpoint of improving the solubility of the resin relative to 100 parts by mass of the component (A), in terms of obtaining a moderate film thickness In view of this, it is preferably 1800 parts by mass or less, and more preferably 1500 parts by mass or less.

The photosensitive resin composition of the present invention may optionally contain a low-molecular compound having a phenolic hydroxyl group within a range that does not reduce the shrinkage residual film rate after curing. By containing a low-molecular compound having a phenolic hydroxyl group, adjustment of alkali solubility during pattern processing becomes easy.

For the purpose of exhibiting the aforementioned effects, the content of the preferred low-molecular compound having a phenolic hydroxyl group relative to 100 parts by mass of component (A) is preferably 0.1 part by mass or more, more preferably 1 part by mass As described above, from the viewpoint of maintaining mechanical properties such as elongation, it is preferably 30 parts by mass or less, and more preferably 15 parts by mass or less.

The photosensitive resin composition of the present invention may optionally contain a thermal crosslinking agent. As for the thermal crosslinking agent, a compound having at least two alkoxymethyl groups and/or hydroxymethyl groups, and a compound having at least two epoxy groups and/or propylene oxide groups can preferably be used, but it is not limited to And so on. By containing these compounds, during the curing after patterning, the condensation reaction with the component (A) forms a cross-linked structure, and the mechanical properties such as elongation of the cured film are improved. In addition, two or more types of thermal crosslinking agents can be used, thereby enabling wider designs.

Preferred examples of compounds having at least two alkoxymethyl groups and/or hydroxymethyl groups include: DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML -PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC , DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML -BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are trade names, Honshu Chemical Industrial (Stock) System), "NIKALAC" (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (the above are the trade names, Sanwa Chemical (Share) system), which can be obtained from various companies. Two or more kinds of these may be contained.

In addition, preferred examples of compounds having at least two epoxy groups and/or propylene oxide groups include, for example, bisphenol A epoxy resin, bisphenol A propylene oxide resin, and bisphenol F Type epoxy resin, bisphenol F type propylene oxide resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl (glycidoxypropyl) silicone, etc. containing epoxy Base polysiloxane, but not limited to these.

Specifically, it can include: "EPICLON" (registered trademark) 850-S, EPICLON HP-4032, EPICLON HP-7200, EPICLON HP-820, EPICLON HP-4700, EPICLON EXA-4710, EPICLON HP-4770, EPICLON EXA -859CRP, EPICLON EXA-1514, EPICLON EXA-4880, EPICLON EXA-4850-150, EPICLON EXA-4850-1000, EPICLON EXA-4816, EPICLON EXA-4822 (the above are trade names, Dainippon Ink Chemical Industry Co., Ltd.) (Trademark), "RIKARESIN" (registered trademark) BEO-60E (trade name, Nippon Physicochemical Co., Ltd.), EP-4003S, EP-4000S (trade name, ADEKA (stock) system), etc., available from each company . Two or more kinds of these may be contained.

The content of the thermal crosslinking agent used in the present invention is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more relative to 100 parts by mass of the component (A). From the viewpoint of maintaining mechanical properties such as elongation, it is preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 70 parts by mass or less, and particularly preferably 40 parts by mass. Parts by mass or less.

烷等醚類。 In order to improve the wettability with the substrate, the photosensitive resin composition of the present invention may optionally contain surfactants, esters such as ethyl lactate or propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl alcohol, etc. Ketones such as methyl isobutyl ketone, tetrahydrofuran, two

Alkanes and other ethers.

The preferable content of these compounds for improving the wettability with the substrate is 0.001 parts by mass or more with respect to 100 parts by mass of the component (A), and from the viewpoint of obtaining a moderate film thickness, it is preferably 1800 parts by mass or less, and more Preferably, it is 1500 parts by mass or less.

The photosensitive resin composition of the present invention may contain inorganic particles. Preferred specific examples include silicon oxide, titanium oxide, barium titanate, aluminum oxide, talc, etc., but are not limited to these.

From the viewpoint of photosensitivity, the average primary particle diameter of these inorganic particles is preferably 1 nm or more and 100 nm or less, more preferably 10 nm or more and 60 nm or less. The individual particle size of these inorganic particles can be measured with a scanning electron microscope, for example, a scanning electron microscope manufactured by JEOL Ltd., JSM-6301NF. In addition, the average primary particle size is calculated by measuring the diameters of 100 particles randomly selected from the photos and finding the arithmetic average.

In addition, in order to improve the adhesion to the silicon substrate, trimethoxyaminopropylsilane, trimethoxyepoxysilane, trimethoxyvinylsilane, and trimethoxy silane may be contained within a range that does not impair storage stability. Silane coupling agents such as thiol propyl silane.

The preferable content of these compounds for improving the adhesion to the silicon substrate is 0.01 parts by mass or more with respect to 100 parts by mass of the component (A), and from the viewpoint of maintaining mechanical properties such as elongation, it is preferably 5 parts by mass or less.

The viscosity of the photosensitive resin composition of the present invention is preferably 2 to 5000 mPa·s. By adjusting the solid content concentration to make the viscosity above 2mPa‧s, the required film thickness can be easily obtained. On the other hand, if the viscosity is 5000 mPa·s or less, it is easy to obtain a highly uniform coating film. A resin composition system having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5-60% by mass.

Next, the method of forming a resin pattern using the photosensitive resin composition of this invention is demonstrated.

When the photosensitive resin composition of the present invention is directly coated on a substrate, wafers such as silicon, ceramics, gallium arsenide, or the like, or a substrate formed by using metals as electrodes and wiring on the substrate can be used. Not limited to this. As for the coating method, there are methods such as spin coating, spray coating, and roll coating using a spinner. In addition, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, etc., but the coating is usually applied so that the film thickness after drying becomes 0.1 to 150 µm. In order to improve the adhesion between the substrate such as a silicon wafer and the photosensitive resin composition, the substrate can also be pre-treated with the aforementioned silane coupling agent. For example, to dissolve 0.5-20% by mass of the silane coupling agent in isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and adipic acid two Solvents such as ethyl esters are surface treated by spin coating, dipping, spray coating, steam treatment, etc. In some cases, after the surface treatment, a heat treatment of 50 to 300°C is carried out to proceed the reaction between the substrate and the silane coupling agent.

Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition film. Drying is preferably carried out at a temperature of 50~150℃ for 1 minute to several hours using an oven, hot plate, infrared rays, etc.

On the other hand, when the photosensitive resin composition of the present invention is used as a photosensitive resin sheet, it is preferable to coat and dry the support film to form a photosensitive resin sheet. The supporting film used is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. In order to improve adhesion and peelability, surface treatments such as polysiloxane, silane coupling agent, aluminum chelating agent, polyurea, etc. can be applied to the bonding surface of the support film and the photosensitive resin sheet. In addition, the thickness of the support film is not particularly limited, but from the viewpoint of workability, it is preferably in the range of 10 to 100 μm. The photosensitive resin composition coated on the support film undergoes a drying step. From the standpoint of drying properties, the drying temperature is preferably 50°C or higher, and from the standpoint of not impairing photosensitivity, the drying temperature is preferably 150 ℃ below. At this time, from the viewpoint of gap filling perfornance at the time of lamination, the film thickness of the photosensitive resin sheet is preferably 5 μm or more. From the viewpoint of film thickness uniformity, the photosensitive resin sheet The thickness of the film is preferably 150 μm or less.

In addition, in order to protect the surface, the photosensitive resin sheet of the present invention may have a protective film on the resin sheet. Thereby, the surface of the photosensitive adhesive film can be protected from pollutants such as dust or dust in the atmosphere.

As for the protective film, a polyolefin film, a polyester film, etc. are mentioned. The protective film preferably has a small adhesive force with the photosensitive resin sheet.

The obtained photosensitive resin sheet is bonded to the substrate. As for the substrate, a wafer such as silicon, ceramics, gallium arsenide, or the like, or a metal formed on it as electrodes and wirings can be used, but it is not limited to these. When the photosensitive resin sheet has a protective film, the photosensitive resin sheet is peeled off, the photosensitive resin sheet and the substrate are opposed to each other, and they are bonded by thermocompression bonding to obtain a photosensitive adhesive composition film. The thermocompression bonding system can be performed by thermocompression processing, thermal lamination processing, thermal vacuum lamination processing, or the like. From the standpoint of adhesion to the substrate and filling properties, the bonding temperature is preferably 40°C or higher. In addition, the photosensitive adhesive film is cured during bonding, and in order to prevent deterioration of the resolution of pattern formation in the exposure and development steps, the bonding temperature is preferably 150° C. or less.

Next, the photosensitive resin composition film formed on the substrate using the above-mentioned method is irradiated with actinic rays through a mask having a desired pattern for exposure. As for the actinic rays used for exposure, there are ultraviolet rays, visible rays, electron rays, X-rays, etc., but in the present invention, the i-line (365nm), h-line (405nm), g-line ( 436nm) is preferred.

In order to form a pattern of heat-resistant resin, a developer solution is used to remove the exposed part after exposure. As for the developing solution, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methyl Amine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc. present alkali An aqueous solution of a sexual compound. Also, in some cases, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfide, Polar solvents such as γ-butyrolactone and dimethylacrylamide, alcohols such as methanol, ethanol, isopropanol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone Ketones, such as ketones, isobutyl ketone, methyl isobutyl ketone, etc., are added to these alkaline aqueous solutions alone or in combination. After developing, it is better to use water for rinsing treatment. Among them, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate, and propylene glycol monomethyl ether acetate, etc. may be added to the water for rinsing treatment.

唑閉環反應，提高耐熱性及耐化學性。在選定溫度進行階段式升溫或是選擇某個溫度範圍進行連續式升溫的同時，實施該加熱處理5分鐘至5小時。就其中一例來說，係在130℃、200℃下分別進行各30分鐘的熱處理。或是可列舉花費2小時從室溫直線升溫至400℃等的方法。 After developing, apply a temperature of 150~500℃ to make the thermal crosslinking reaction, the imine ring-closure reaction,

The azole ring-closure reaction improves heat resistance and chemical resistance. The heat treatment is performed for 5 minutes to 5 hours while the temperature is selected for stepwise heating or a certain temperature range is selected for continuous heating. For one example, heat treatment was performed at 130°C and 200°C for 30 minutes each. Alternatively, a method of linearly raising the temperature from room temperature to 400°C over 2 hours can be cited.

The heat-resistant resin film formed using the photosensitive resin composition of the present invention is suitable for use in passivation films of semiconductors, protective films of semiconductor elements, interlayer insulating films of multilayer wiring for high-density packaging, and insulating layers of organic electroluminescent elements. .

[Example]

Examples are listed below to illustrate the present invention, but the present invention is not limited by these examples. First, the evaluation methods in the respective examples and comparative examples will be described. In the evaluation of the photosensitive resin composition (hereinafter referred to as varnish), a varnish filtered in advance with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries Co., Ltd.) was used.

(1) Determination of the content of (C) compound in the photosensitive resin composition (varnish)

0.03 g of (A) component polymerized with (C) compound and 0.01 g of 3-nitrobenzoic acid methyl ester as an internal standard material were dissolved in 0.7 g of deuterated dimethyl sulfoxide, and NMR (Japan Electronics ( Stock) system, GX-270) for analysis. Using the area of the peak near 3.9 ppm derived from methyl 3-nitrobenzoate as a reference, the amount of the (C) compound contained in the (A) component was quantified from each peak area.

(2) Calculation of the total content of (C) compound in the cured film

Using the coating and developing device Mark-7 (manufactured by TOKYO ELECTRON Co., Ltd.), the varnish was applied on an 8-inch silicon wafer by spin coating and baked on a hot plate at 120°C for 3 minutes to produce a film thickness of 3.2μm Of pre-baked film. After that, using the aforementioned Mark-7 developing device, developing with 2.38 parts by mass of a tetramethylammonium aqueous solution (the following 2.38% TMAH, manufactured by Tama Chemical Industry Co., Ltd.), rinsed with distilled water, and dried thoroughly to display The post-image solid film was cured at 200°C for 60 minutes in a nitrogen atmosphere to obtain a cured film.

The film thickness of the obtained cured film was measured, and it was cut into 1x5cm, and it adsorbed and trapped by the air blowing trap method. Specifically, helium gas is used as a purge gas to heat the collected cured film at 400° C. for 60 minutes, and the desorbed components are collected in the adsorption tube.

Use a thermal desorption device to thermally desorb the captured components under the primary desorption condition at 260°C for 15 minutes, and under the secondary adsorption and desorption conditions at -27°C and 320°C for 5 minutes, then use GC- The MS device 7890/5975C (manufactured by Agilent) performs GC-MS analysis under the conditions of column temperature: 40 to 300° C., carrier gas: helium (1.5 mL/min), and scanning range: m/Z 29 to 600. A calibration curve was created by analyzing GC-MS in each component of the compound (C) under the same conditions as above to calculate the amount of gas generated.

Divide the obtained value (μg) by the area of 5 cm ² to obtain μg/cm ² . This value is divided by the specific gravity of the alkali-soluble resin (a) and the film thickness is multiplied by 100 times to calculate the total content of the compound (c) in the cured film.

(3) Measuring method of film thickness

After pre-baking, Lambda Ace STM-602 manufactured by Dainippon Screen Co., Ltd. was used to measure the refractive index of the pre-baked film at 1.629 based on polyimide, and the refractive index of the cured film at 1.773.

(4) Adhesion test

The adhesion test with metal materials was performed in the following method.

<Production of hardened film>

Copper is sputtered on the silicon wafer, and substrates (copper sputtered substrates) each having a metal material layer formed with a thickness of 200 nm on the surface are prepared. A spinner (manufactured by MIKASA Co., Ltd.) was used to apply the varnish on the substrate by a spin coating method, and then a hot plate (D-SPIN by Dainippon Screen Co., Ltd.) was used to bake at 120°C for 3 minutes to produce the final thickness 8μm prebaked film. For the negative photosensitive resin composition, an i-line stepper NSR-2005i9C (manufactured by Nikon Corporation) was then used to expose the entire surface of the substrate at an exposure amount of ^{1000 mJ/cm 2.} For these films, use a dust-free oven (CLH-21CD-S manufactured by KOYO THERMO Systems Co., Ltd.), and cure at 140°C for 30 minutes under nitrogen gas flow (oxygen concentration below 20ppm), then heat up and cure at 200°C In 1 hour, a photosensitive resin cured film was obtained.

<Evaluation of Adhesion Characteristics>

The substrate is divided into two, and for each substrate, a single-edged knife is used to engrave the cured film into a grid of 10 rows and 10 columns at 2 mm intervals. Using one of the sample substrates, the peeling using cellophane tape was used to calculate how many squares were peeled off among 100 squares, and the adhesion characteristics between the metal material and the resin cured film were evaluated. In addition, for another sample substrate, a Pressure Cooker Test (PCT) device (HAST CHAMBER EHS-211MD manufactured by TABAI ESPEC Co., Ltd.) was used, and the PCT treatment was performed at 121°C and 2 atmospheres of saturation conditions. After hours, the above-mentioned peeling test was performed. For each substrate, the number of peeled pieces in the peel test was less than 10 as A, 10 or more and less than 20 as B, and 20 or more as C.

(5) Evaluation of coatability

The varnish was spin-coated on a substrate with a height difference, and then baked on a hot plate at 120°C (using a coating and developing device Act-8 manufactured by TOKYO ELECTRON (Stock)) for 3 minutes to produce a pre-baked film with an average thickness of 10 μm. The prebaked film was irradiated with a sodium lamp, and the surface was observed visually. If there is no vertical streaks, it is regarded as ○, and if there are vertical streaks, it is regarded as x. Next, a field emission scanning electron microscope (S-4800 manufactured by Hitachi High-Technologies Co., Ltd.) was used to observe the cross section of the height difference of the substrate, and to measure the height difference of the prebaked film covering the substrate and the upper half of the buried part. The thickness of the film. The measurement points were divided into 30 parts from the periphery of the substrate after the 10 mm wide side was removed from each side, and the number was determined to be 30 points. The landfill property of the height difference is calculated by the following formula.

Maximum height = the total average of the height of the height difference on the substrate and the film thickness of the prebaked film covering it

The film thickness of the buried part = the average value of the film thickness in the center of the buried part

Landfillability (%)=[maximum height/film thickness of buried part]×100

Here, the landfillability is preferably 90-100%, and more preferably 95-100%. The landfill property is evaluated by taking the case of 95% or more and 100% as A, the case of 90 or more and less than 95% as B, and the case of less than 90% as C.

The substrate with height difference used in the evaluation was produced by the following method. An OFPR (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) film is formed as a photoresist on an 8-inch silicon wafer, and the pattern is formed by a photoetching method. The pattern is used as a mask, and an etching device (RIE- 10N) Dry etching is performed, and the pattern composed of OFPR is peeled off with acetone to form a height difference with a depth of 4 μm.

[Synthesis Example 1] Synthesis of Diamine Compound (HA)

Dissolve 164.8g (0.45mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) in 900mL of acetone, 156.8g (2.7mol) of 1, In 2-propylene oxide, cool to -15°C. A solution prepared by dissolving 183.7 g (0.99 mol) of 3-nitrobenzyl chloride in 900 mL of acetone was dropped. After the dropping, the reaction was carried out at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered out and dried in vacuum at 50°C.

270 g of the solid was charged into a 3L stainless steel autoclave, dispersed in 2400 mL of methyl ceroxu, and 5 g of 5% palladium-carbon was added. The hydrogen gas is introduced into it with a balloon, and the reduction reaction is carried out at room temperature. After 2 hours, the reaction was terminated after confirming that the balloon would no longer deflate. After the completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a diamine compound represented by the following formula (hereinafter referred to as HA).

[Synthesis example 2] Synthesis of polyimide resin (A-1)

Under a stream of dry nitrogen, 62.04 g (0.2 mol) of bis(3,4-dicarboxyphenyl) ether dianhydride (hereinafter referred to as ODPA) was dissolved in 1000 g of N-methyl-2-pyrrolidone (hereinafter referred to as ODPA). Called NMP). Among them, 58.60 g (0.16 mol) of BAHF, 12.00 g (0.02 mol) of ED-600 (trade name, manufactured by HUNTSMAN (stock)), and 4.37 g (0.04 mol) of 3-aminophenol as the end-capping material were added. Ear) was added together with 250 g of NMP, and reacted at 60°C for 1 hour, and then at 160°C for 6 hours. After the completion of the reaction, the solution was cooled to room temperature, and the solution was poured into 10 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80°C for 40 hours to obtain a polyimide resin (A-1).

[Synthesis example 3] Synthesis of polyimide resin (A-2)

The polymerization solvent of Synthesis Example 2 was changed from NMP to 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as DMI), and synthesis was carried out in the same manner as Synthesis Example 2 to obtain polyimide resin (A-2 ). As a result of NMR analysis, the content of DMI was 3.0 parts by mass with respect to 100 parts by mass of the polyimide resin (A-2).

[Synthesis example 4] Synthesis of polyimide resin (A-3)

The polymerization solvent of Synthesis Example 2 was changed from NMP to 3-methoxy-N,N-dimethylpropanamide (hereinafter referred to as Equamide M100), and synthesis was carried out in the same manner as Synthesis Example 2 to obtain a polyimide resin (A-3). As a result of NMR analysis, the content of Equamide M100 was 2.8 parts by mass with respect to 100 parts by mass of the polyimide resin (A-3).

[Synthesis example 5] Synthesis of polyimide resin (A-4)

The polymerization solvent of Synthesis Example 2 was changed from NMP to N,N-dimethyl propylene urea (hereinafter referred to as DMPU), and synthesis was performed in the same manner as Synthesis Example 2 to obtain polyimide resin (A-4). As a result of NMR analysis, the content of DMPU was 3.1 parts by mass with respect to 100 parts by mass of the polyimide resin (A-4).

[Synthesis example 6] Synthesis of polyimide resin (A-5)

The polymerization solvent of Synthesis Example 2 was changed from NMP to 3-butoxy-N,N-dimethylpropanamide (hereinafter referred to as Equamide B100), and synthesis was performed in the same manner as Synthesis Example 2 to obtain a polyimide resin (A-5). As a result of NMR analysis, the content of Equamide B100 was 3.2 parts by mass with respect to 100 parts by mass of the polyimide resin (A-5).

[Synthesis example 7] Synthesis of polyimide precursor resin (A-6)

Under a stream of dry nitrogen, 62.04 g (0.2 mol) of ODPA was dissolved in 1000 g of NMP. In it, 96.72g (0.16 mol) of HA and 4.97g (0.02 mol) of 1,3-bis(3-aminopropyl) tetramethyldisiloxane and 100g of NMP were added together, at 20 The reaction was carried out at °C for 1 hour, followed by the reaction at 50 °C for 2 hours. Next, 4.37 g (0.04 mol) of 3-aminophenol as a blocking agent was added together with 30 g of NMP, and the reaction was carried out at 50°C for 2 hours. Thereafter, a solution obtained by diluting 47.66 g (0.4 mol) of N,N-dimethylformamide dimethyl acetal with 50 g of NMP was dropped over 10 minutes. After dropping, it was stirred at 50°C for 3 hours. After the stirring was completed, after cooling the solution to room temperature, the solution was poured into 1 L of water to obtain a precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80°C for 20 hours to obtain a powder of a polyimide precursor resin (A-6).

[Synthesis Example 8] Synthesis of polyamide resin (A-7)

唑前驅物)。 Under a stream of dry nitrogen, 88.64g (0.18 mol) of dicarboxylic acid diester composed of 4,4'-dicarboxydiphenyl ether and 1-hydroxybenzotriazole, BAHF 65.93g (0.18 mol), ED -600 (trade name, manufactured by HUNTSMAN Co., Ltd.) 12.00 g (0.02 mol) and 800 g of NMP were reacted at 25°C for 30 minutes, then heated in an oil bath, and reacted at 80°C for 8 hours. Next, 12.31 g (0.075 mol) of 5-norbornene-2,3-dicarboxylic anhydride as a blocking agent was added, and the reaction was terminated after further stirring at 80°C for 3 hours. After the completion of the reaction, the solution was cooled to room temperature, the reaction mixture was filtered, and the reaction mixture was poured into a mixture of 2L of water/isopropanol=3/1 (volume ratio) to obtain a precipitate. The precipitate was collected by filtration, washed with water three times, and dried in a vacuum dryer at 80°C for 20 hours to obtain polyamide resin (A-7) (polybenzo

Azole precursors).

[Synthesis Example 9] Synthesis of quinonediazide compound (b-2-1)

烷1000g中。一面用冰冷卻反應容器，一面將混合有1,4-二

烷150g與三乙胺14.53g(0.14莫耳)的液體滴入以不達到35℃以上的系統內。滴入後，在30℃下攪拌2小時。過濾三乙胺鹽，將濾液投入7L的純水中得到沉澱。藉由過濾收集此沉澱，再以1質量%鹽酸2L洗淨。之後，再以5L的純水洗淨2次。在50℃的真空乾燥機中將此沉澱乾燥24小時，得到Q之中平均2個為經5-萘醌二疊氮磺酸酯化之以下述式表示之醌二疊氮化合物(b-2-1)。 Under a stream of dry nitrogen, 20 g of TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 5-naphthoquinone diazide sulfonyl chloride (NAC-5, manufactured by Toyo Gosei Co., Ltd.) 35.08 g (0.131) Mol) dissolved in 1,4-di

Ethane in 1000g. Cool the reaction vessel with ice on one side, and mix with 1,4-di

A liquid of 150 g of alkane and 14.53 g (0.14 mol) of triethylamine was dropped into the system not to reach 35°C or higher. After dropping, it was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into 7 L of pure water to obtain a precipitate. The precipitate was collected by filtration, and washed with 2 L of 1% by mass hydrochloric acid. After that, wash it twice with 5L of pure water. The precipitate was dried in a vacuum dryer at 50°C for 24 hours, and an average of 2 of Q was esterified with 5-naphthoquinone diazide sulfonic acid and represented by the following formula (b-2 -1).

Also, the names and structures of the compounds shown in Table 1 to Table 3 are listed below.

b-1-1: 1,9-nonanediol dimethacrylate

b-1-2: 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzyloxime) (OXE02)

C-1: δ-valerolactone (boiling point 230℃)

C-2: Diethylene glycol butyl ether (boiling point: 230°C)

C-3: 2-phenoxyethanol (boiling point: 245°C),

C-4: 1,3-Dimethyl-2-imidazolidinone (boiling point: 220°C)

C-5: 3-Methoxy-N,N-dimethylpropanamide (boiling point: 216°C)

C-6: N,N-dimethyl allyl urea (boiling point 246℃)

C-7: 3-Butoxy-N,N-dimethylpropanamide (boiling point: 252°C)

C-8: N-cyclohexyl-2-pyrrolidone (boiling point: 154°C/7mmHg, when converted to boiling point at normal pressure: 305°C),

C-9: N,N-dimethylformamide (boiling point: 153°C)

D-1~D-5: The following formula

E-1, E-2: the following formula

F-1: HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), a thermal crosslinking agent for alkoxymethyl compounds with acidic groups

[Examples 1 to 53, Comparative Examples 1 to 6]

Hereinafter, Example 1 will be given as an example for specific description. To the obtained resin (A-2) 10g was added (b-1-1) 1.5g and (b-1-2) 3.0g as (B) sensitizer, and (C-1) as (C) ) 0.30 g, 20 g of γ-butyrolactone (GBL) as a solvent was added to produce a varnish. Similarly, for Examples 2 to 53, and Comparative Examples 1 to 6, varnishes were produced with the compositions shown in Tables 1 to 3. The characteristics of the produced varnish were measured using the above-mentioned evaluation method, and the obtained results are shown in Tables 4-6. In addition, all the solvents of Examples 1 to 53, and Comparative Examples 1 to 6 were implemented with 20 g of GBL.

By adding the compound (C), the coating properties and adhesion can be improved. On the other hand, in C-9: N,N-dimethylformamide (boiling point: 153°C), no improvement in coatability and adhesion was seen.

Claims (17)

A photosensitive resin composition containing (A) an alkali-soluble resin having an organic group derived from an aliphatic diamine, (B) a photosensitizer, and (C) a liquid under the conditions of 1013 hPa and 25°C and a boiling point of 210°C The above compound is characterized in that, with respect to 100 parts by mass of (A) an alkali-soluble resin having an organic group derived from aliphatic diamine, the (C) containing 0.1 to 15 parts by mass is at 1013 hPa and 25°C. Liquid compound with a boiling point of 210°C or higher. The compound (C) that is liquid at 1013hPa and 25°C and has a boiling point of 210°C or higher is selected from the compounds represented by general formulas (1) to (4) More than one compound,

(In the general formulas (1)~(4), R ¹ represents hydrogen or an alkyl group with 1 to 5 carbons, R ² represents a divalent organic group with 1 to 5 carbons, and R ⁵ represents hydrogen or a carbon number. 1 to 5 organic groups, R ³ , R ⁴ , and R ⁶ each independently represent an organic group having 1 to 5 carbon atoms, and n represents an integer in the range of 1 to 3). The photosensitive resin composition according to claim 1, wherein the (A) alkali-soluble resin having an organic group derived from an aliphatic diamine comprises a polyimide, a polybenzo

One or more resins among azoles, polyamide imides, and these precursors. The photosensitive resin composition of claim 1 or 2, wherein the (B) photosensitizer is a photopolymerization initiator and a polymerizable unsaturated compound. The photosensitive resin composition of claim 1 or 2, wherein the (B) photosensitizer is a quinonediazide compound. The photosensitive resin composition of claim 1 or 2, which further contains (D) a compound represented by the general formula (5),

(In the general formula (5), R ⁷ to R ⁹ represent any one of an oxygen atom, a sulfur atom, or a nitrogen atom, ^{and at least one of R 7} to R ⁹ represents a sulfur atom; l represents 0 or 1; when l is 0, R ⁷ represents an oxygen atom or a sulfur atom, when l is 1, R ⁷ represents a nitrogen atom; m and n represent 1 or 2; R ¹⁰ ~R ¹² represent each independently A hydrogen atom or an organic group with 1 to 20 carbon atoms). The photosensitive resin composition of claim 1 or 2, which further contains (E) a compound represented by the general formula (6),

(In the general formula (6), R ¹³ represents a hydrogen atom or an alkylene group having 1 or more carbon atoms, R ¹⁴ represents an alkylene group having 2 or more carbon atoms, and R ¹⁵ represents an alkylene group having at least 2 carbon atoms. , Oxygen atom, and nitrogen atom any one of 1-4 valence organic groups, k represents an integer of 1 to 4). A photosensitive resin sheet, which is a photosensitive resin sheet formed of the photosensitive resin composition according to any one of claims 1 to 6. A cured film, which is a cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 6 or the photosensitive resin sheet according to claim 7. Such as the cured film of claim 8, which contains 0.005 mass% or more and 5 mass% or less of the compound (C) which is liquid under the conditions of 1013 hPa and 25°C and has a boiling point of 210°C or higher. A method for manufacturing a relief pattern of a cured film, comprising: coating the photosensitive resin composition according to any one of claims 1 to 6 on a substrate or applying the photosensitive resin sheet according to claim 7 Laminating on a substrate and drying to form a photosensitive resin film; a step of exposing the photosensitive resin film through a mask; a step of developing the exposed photosensitive resin film with an alkaline solution; and after developing The photosensitive resin film is heat-treated. The method for producing a concave-convex pattern of a cured film according to claim 10, wherein the step of coating the photosensitive resin composition on a substrate and drying to form a photosensitive resin film includes a step of coating on the substrate using a slit nozzle. An organic EL display device in which the hardened film of claim 8 or 9 is arranged on the planarization layer on the driving circuit and the insulating layer on the first electrode At least one of them. A semiconductor device provided with a cured film as in Claim 8 or 9 as an interlayer insulating film between rewiring rooms. The semiconductor device of claim 13, wherein the rewiring is a copper metal wiring, and the width of the copper metal wiring and the interval between adjacent wirings are both 5 μm or less. A semiconductor device in which the cured film of claim 8 or 9 is arranged on a sealing resin substrate provided with a silicon wafer as an interlayer insulating film between rewiring. A method of manufacturing a semiconductor device, comprising: arranging the cured film of claim 8 or 9 on a support substrate provided with a temporary adhesive material as an interlayer insulating film in a rewiring room, arranging a silicon wafer thereon, and sealing The resin step, and then the step of peeling off the support substrate with the temporary adhesive material and the redistribution. A semiconductor device is provided with a cured film as in Claim 8 or 9 as an interlayer insulating film of adjacent substrates made of two or more materials.