TW201921111A - Photosensitive resin composition, photosensitive sheet, cured film thereof, manufacturing method therefor, and hollow construct and electronic component using same - Google Patents

Abstract

Provided is a photosensitive resin composition having excellent pattern workability. A cured film derived by curing same has high chemical resistance, high elasticity, high ductility, and high adhesion to metal, especially copper. The present invention contains (A) at least one type of resin selected from polybenzoxazoles and polyimides having branches on the main chain, as well as precursors thereof, (B) a photopolymerization initiator, and (C) a compound having two or more ethylenically unsaturated bonds. The ratio of structural units in the resin (A) that constitute branching points on the main chain to all structural units is 0.05-12 mol% (inclusive).

Description

   Photosensitive resin composition, photosensitive sheet and hardened film thereof, method for manufacturing the same, hollow structure using the same, and electronic parts   

The present invention relates to a photosensitive resin composition, a photosensitive sheet, a cured film thereof, and a method for producing the same. More specifically, it relates to a photosensitive resin composition suitable for use as a surface protection film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescence element, and the like, a cured film thereof, and a method for producing the same.

As representative materials for surface protection films, interlayer insulating films of semiconductor devices, insulating layers of organic electrolytic devices, and flattening films of TFT substrates, for example, polyimide-based resins having excellent heat resistance and electrical insulation properties can be mentioned. . In addition, in order to improve productivity, there has also been a review of photosensitive polyimide and its precursors that have been provided with photosensitivity. This photosensitive resin composition is classified into two types, a positive material and a negative material, according to a method of forming a pattern. The former "positive type" is a method of obtaining a pattern by exposing the exposure portion to be soluble in a developing solution; the latter "negative type" is a method of obtaining a pattern by exposing the exposure portion to be insoluble in a developing solution.

Negative-type photosensitive polyimide-based materials can be roughly classified into "ester types" using a polyethylenic unsaturated group-based polyimide as a matrix polymer (Patent Document 1), and the use of ethylene having ionic bonds The "ionic type" of poly (amino acid) having an unsaturated bond (Patent Document 2). Materials based on these technologies have been used in the production of various electronic parts. Since these organic solvents are used as a developing solution, the environmental load such as VOC (Volatile Organic Compounds) is large, but the cured film has excellent characteristics. Furthermore, a negative photosensitive polyfluorene imine resin composition using an alkaline aqueous solution as a developing solution has also been proposed (Patent Document 3). Compared with organic solvent development, this technology has a smaller environmental load.

A positive photosensitive polyimide material has been proposed as a positive photosensitive resin composition containing a hydroxystyrene resin, a polyamidic acid, and a quinonediazide compound (Patent Document 4). This resin composition has a strong interaction with a phenolic hydroxyl group of a hydroxystyrene resin in an unexposed portion and a quinonediazide compound, and thus suppresses solubility in an alkaline solution belonging to a developing solution. On the other hand, in the exposure section, the quinonediazide compound generates light using light to significantly increase the solubility in the alkaline solution. Since the unexposed portion and the exposed portion have poor solubility in an alkaline solution, a positive relief pattern can be made.

    [Prior technical literature]         [Patent Literature]    

Patent Document 1: Japanese Patent Laid-Open No. 51-40922

Patent Document 2: Japanese Patent Laid-Open No. 54-145794

Patent Document 3: International Publication No. 2004/109403

Patent Document 4: Japanese Patent Laid-Open No. 2007-156243

In recent years, with the expansion of the use of semiconductors and the improvement of performance, countermeasures have been spread to reduce costs and increase integration due to the efficiency of manufacturing steps. Therefore, attention has been focused on a semiconductor device that forms a multilayer metal rewiring. The insulation film between metal heavy wiring requires resistance to a photoresist peeling liquid for chemical resistance. In addition, by forming a plurality of layers, the stress on the material is increased as compared with the conventional one. Therefore, a material with a high elongation that does not cause a break point even under high stress is required. In the bump electrode formation step described later, in order to protect the underlying semiconductor element, it is necessary to have sufficient hardness, that is, a high elastic modulus. However, the above-mentioned materials are not in a state of good processability, and the cured film which has been hardened at the same time has photoresistance resistance, high elastic modulus, and high elongation at a high level. The reason is that regardless of the negative type and the positive type, if a large amount of cross-linking agent is introduced in order to improve the drug resistance and the elastic modulus, there will be a trade-off relationship that leads to a decrease in elongation.

In order to solve the problems associated with the conventional technology as described above, the present invention provides a photosensitive resin composition capable of forming a good pattern by using a general optical lithography step, and a cured cured film having a high elastic modulus and a high elongation.

To solve the above problems, the present invention relates to the following inventions.

That is, a photosensitive resin composition containing (A) polyfluorene imine and polybenzo with a branch from a main chain. Among the azoles and these precursors, one or more resins, (B) a photopolymerization initiator, and (C) a compound having two or more ethylenically unsaturated bonds are selected; among them, the main chain in the (A) resin The structural unit of the branch point is a ratio of 0.05 mol% to 12 mol% in the whole structural unit.

Furthermore, a method for manufacturing a cured film includes the steps of coating the photosensitive resin composition on a substrate, or laminating the photosensitive sheet on a substrate, and drying to form a photosensitive resin film. A step of exposing the photosensitive resin film; a step of applying heat treatment to the exposed photosensitive resin film; a step of developing the photosensitive resin film after heat treatment; and a photosensitive resin after development The film is subjected to a heat treatment step.

The present invention also relates to an interlayer insulating film, a semiconductor protective film, and an electronic component in which the cured film is disposed.

The photosensitive resin composition and the photosensitive sheet of the present invention have good pattern processability, and a cured film system cured by the same has a high elongation and an elastic modulus. In addition, the electronic component of the present invention has an insulating film pattern excellent in adhesion and chemical resistance, and has high reliability.

1‧‧‧ silicon wafer

2‧‧‧Al pad

3‧‧‧ passivation film

4‧‧‧ insulating film

5‧‧‧metal (Cr, Ti, etc.) film

6‧‧‧ Metal wiring (Al, Cu, etc.)

7‧‧‧ insulating film

8‧‧‧ barrier metal

9‧‧‧ cutting road

10‧‧‧Solder bump

11‧‧‧ silicon wafer

12‧‧‧ first floor (pillar floor)

13‧‧‧ 2nd floor (roof floor)

FIG. 1 is an enlarged sectional view of a pad portion of a semiconductor device having bumps.

FIGS. 2a to f are detailed manufacturing method diagrams of semiconductor devices having bumps.

FIG. 3 is a cross-sectional view of a hollow structure formed on a silicon wafer.

4a and b are diagrams of a method for manufacturing a hollow structure formed on a silicon wafer.

The photosensitive resin composition provided by the present invention is provided with: (A) a polyimide and a polybenzo with a branch from a main chain; One or more resins are selected from azole and these precursors; (B) a photopolymerization initiator; and (C) a compound having two or more ethylenically unsaturated bonds. Hereinafter, each component is demonstrated.

The photosensitive resin composition of the present invention contains: (A) polyfluorene and polybenzo with a branch from a main chain One or more resins are selected from azole and these precursors. In addition, the structural unit that becomes the branch point of the main chain in the (A) resin accounts for a ratio of 0.05 mol% or more and 12 mol% or less of the total structural unit composed of a terminal and an intramolecular repeating unit (hereinafter also referred to as "(A) ingredient"). When the component (A) has a branch in this range, a cured film having a high elongation and a high elastic modulus can be obtained. The reason is that it is presumed that by having branches, the entanglement of polymers will increase. If it exceeds the range, the elastic modulus is improved, but the elongation is not easy to increase. If it is lower than this range, the effect of increasing the elongation and elastic modulus cannot be fully obtained.

Here, the polyimide precursor may be, for example, polyamidic acid, polyamidate, polyamidamine or polyisoimide. Polyamines having a tetracarboxylic acid residue and a diamine residue make tetracarboxylic acid or the corresponding tetracarboxylic dianhydride or dicarboxylic acid dicarboxylic acid diester, diamine or the corresponding diisocyanate compound, or tricarboxylic acid. Methyl silylated diamine can be obtained by reaction. The method for introducing a branch into the main chain may be, for example, a method in which an acid component further uses a trivalent or higher polybasic acid anhydride or a polyester chloride compound; an amine component is a method in which a trivalent or higher amine or a corresponding isocyanate compound or a methylsilylamine compound ; Or a method that performs both. Polyimide is obtained by heat-treating polyamic acid, or performing a dehydration closed-loop by chemical treatment with acid, alkali, or the like. More specifically, a solvent that is azeotropic with water, such as m-xylene, may be added and heat-treated, or a weakly acidic carboxylic acid compound may be added and heat-treated at 100 ° C or lower. Examples of the ring-closing catalyst used in the above chemical treatment include dehydration condensation agents such as carboxylic anhydride or dicyclohexylcarbonyldiamidine, and bases such as triethylamine.

Polybenzo The azole precursor system may be, for example, polyhydroxyamidine, polyamidoamine, polyamidoamine or polyamidoimine, and is preferably polyhydroxyamidoamine. Polyhydroxyamidine having a dicarboxylic acid residue and a diaminophenol residue can be obtained by reacting a diaminophenol with a dicarboxylic acid or a corresponding dicarboxylic acid chloride or an active ester of a dicarboxylic acid. . The method for introducing a branch into the main chain may be, for example, a method in which an acid component further uses a trivalent or higher polycarboxylic acid or a corresponding polycarboxylic acid chloride or a polycarboxylic acid active ester; the aminophenol component uses a trivalent or higher amine group. A method of phenol or a corresponding isocyanate phenol compound; or a method of performing both. Polybenzo The azole system can be obtained by subjecting polyhydroxyamidine to dehydration ring closure by heat treatment or chemical treatment. More specifically, a solvent that is azeotropic with water, such as m-xylene, may be added and heat-treated, or an acidic compound may be added and heat-treated at 200 ° C or lower. The closed-loop catalyst system used in the above chemical treatment may be, for example, anhydrous phosphoric acid, a base, or a carbodiimide compound.

The component (A) is preferably a resin containing a structural unit represented by the following general formula (1) or general formula (2). In addition, it may contain two or more types of resins having these structural units, or it may be copolymerized with two or more types of structural units. However, the component (A) is represented by one or more formulas selected from the structural units of l + m ≧ 1 in the general formula (1) or the structural units of h + i ≧ 1 in the general formula (2). The structural unit is preferably a ratio of 0.05 mol% or more and 12 mol% or less (preferably 10 mol% or less) in the resin structural unit. Among them, more preferably 0.5 mol% to 5 mol%. If it is less than 0.05 mol%, the effect of increasing elongation and elastic modulus will be small, and if it exceeds 12 mol%, elongation and elastic modulus will not be able to obtain sufficient effect. In addition, it may be difficult to suppress gelation during production.

(In the formula, X ¹ represents a divalent to 16-valent organic group having 2 or more carbon atoms; Y ¹ represents a divalent to 14-valent organic group having 2 or more carbon atoms; R ¹ and R ² represent each Independent hydrogen or any one of 1 to 20 carbons. P, q, and s represent independent integers of 0 to 4; r represents independent integers of 0 to 6. l and m represent Represents the number of branches in the main chain, each independently representing an integer from 0 to 4. However, l + m ≧ 1. Also, related to l, m, p, q, r, and s, when the value is 0, the functions in parentheses The radicals each represent a hydrogen atom.)

(In the formula, X ² represents a 4-valent to 16-valent organic group having 2 or more carbon atoms; Y ² represents a divalent to 10-valent organic group having 2 or more carbon atoms; R ³ and R ⁴ represent each Any one of independent hydroxyl groups or organic groups having 1 to 20 carbon atoms. T and u represent independent integers of 0 to 4. h and i represent branch numbers of the main chain and each independently represent 0 to 4 Integer. However, h + i ≧ 1. In addition, when the values of h, i, t, and u are 0, the functional groups in parentheses each represent a hydrogen atom.)

In the general formula (1), X ¹ is a residue of a di, tri, tetra, penta, penta, penta, penta, penta, penta, penta, octa or octacarboxylic acid, or a residue derived from a derivative thereof. In the general formula (2), X ² represents a residue of a tetra-, hexa-, octa-, or decacarboxylic acid residue or a derivative thereof (hereinafter, these are collectively referred to as "acid residue"). In addition, when an acid component corresponding to the acid residue is used for polymerization, the acid residue can be contained in a structural unit. Examples of the acid component system using X ¹ as an acid residue include cyclobutanedicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, and isopropylpropane. Diacid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid Acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylene Methyl pimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexafluorosebacate, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid Acid, tetradecanedioic acid, pendecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecenedioic acid, nonadecanedioic acid, eicosenedioic acid, arsenic acid, Arsenic dicarboxylic acid, arsenic dicarboxylic acid, arylenetetracarboxylic acid, arpentalic acid, arcanedioic acid, arcanedioic acid, arcanedioic acid, arcanedioic acid, arsenic Diacid Aliphatic dicarboxylic acids, such as arylene dicarboxylic acid, arylene dicarboxylic acid, diethylene glycol acid; terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl Aromatic dicarboxylic acids such as benzene dicarboxylic acid, diphenyl ketone dicarboxylic acid, or triphenyl dicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, or biphenyl tricarboxylic acid Carboxylic acid; or pyromellitic 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'-diphenylketonetetracarboxylic 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-di Carboxyphenyl) fluorene, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5 Aromatic tetracarboxylic acids such as 1,6-pyridinetetracarboxylic acid or 3,4,9,10-fluorenetetracarboxylic acid; or butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3,4-ring Pentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, bicyclic [2.2.1.] Heptanetetracarboxylic acid, bicyclic [ 3.3.1.] Tetracarboxylic acid, bicyclic [3.1.1.] Hept-2-ene tetracarboxylic acid, bicyclic [2.2.2.] Octane tetracarboxylic acid or aliphatic tetracarboxylic acid such as adamantane tetracarboxylic acid, etc. Wait. Examples of the acid component having a valence of 5 or more include the following compounds:

(In the formula, the complex number R ⁵ represents any one of the following structures.)

In the general formula (2), the acid component having X ² as an acid residue may be, for example, a tetracarboxylic acid and a carboxylic acid compound having a valence of five or more in the specific examples of the acid component having X ¹ as the acid residue.

These acids can be used directly or in the form of anhydride, chloro or active ester. The activated ester system can be structured as follows, for example, but is not limited thereto.

(Where A and B are, for example, a hydrogen atom, methyl, ethyl, propyl, isopropyl, third butyl, trifluoromethyl, halo, phenoxy, nitro, etc .; It's not just limited.)

In addition, the preferable structure of the acid residues of X ¹ and X ² may be, for example, the following structures or 1 to 4 hydrogen atoms of these structures are substituted by an alkyl group, a fluoroalkyl group, or an alkyl group having 1 to 20 carbon atoms. A structure substituted with an oxy group, an ester group, a nitro group, a cyano group, a fluorine atom, or a chlorine atom.

[Chemical 8]

However, J series means direct bonding, -COO-, -CONH-, -CH _2- , -C ₂ H _4- , -O-, -C ₃ H _6- , -SO _2- , -S-,- Si (CH ₃ ) _2- , -O-Si (CH ₃ ) ₂ -O-, -C ₆ H _4- , -C ₆ H ₄ -OC ₆ H _4- , -C ₆ H ₄ -C ₃ H ₆ -C ₆ H _4- , or -C ₆ H ₄ -C ₃ F ₆ -C ₆ H _4- .

Furthermore, by using a silicon atom-containing tetracarboxylic acid such as dimethylsilane diphthalic acid or 1,3-bis (phthalic acid) tetramethyldisilazane, the adhesion to the substrate can be improved and the substrate can be cleaned. Oxygen plasma used, resistance to UV ozone treatment. The di- or tetracarboxylic acid containing silicon atoms preferably uses 1 to 30 mol% of the total acid component.

When (A) component is polybenzo In the case of an azole or a precursor thereof, branching can be introduced into the main chain by polycondensing a carboxylic acid having a trivalent or higher value or a derivative thereof. This introduction method is a method of introducing the general formula (1) into a structural unit having l ≧ 1. Examples of the acid component serving as the branch point include trivalent or higher carboxylic acid compounds in the specific examples of the acid component in which X ¹ is an acid residue. Among them, in order to maintain a high degree of elongation and elastic modulus, it is preferable Trimellitic acid, pyromellitic acid, diphenyl ether tricarboxylic acid, biphenyltricarboxylic acid, pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) fluorene, bis (3,4-dicarboxyphenyl) ether, and the like. When the component (A) is a polyimide or a precursor thereof, a branch can be introduced into the main chain by addition polymerization or polycondensation of a carboxylic acid compound having an valence of 6 or more or an anhydrous substance thereof. The introduction method is a method of introducing a structural unit that becomes l ≧ 1 and r ≧ 3 in the above general formula (1); or a method of introducing a structural unit that becomes h ≧ 1 in the above general formula (2). Specific examples of the acid component that becomes the branch point are, for example, the carboxylic acid compounds having a valence of 6 or more in the specific examples of the acid component with X ¹ as the acid residue. Among them, the following compounds are preferred because they can maintain high elongation and elastic modulus. . In addition, since these can be used as an anhydrous substance and have less by-products, they are preferable.

[Chemical 10]

(In the formula, the complex number R ⁵ represents any one of the following structures.)

In the general formula (1), R ¹ represents any one of hydrogen or an organic group having 1 to 20 carbon atoms. In order to improve the exposure sensitivity, the organic group having 1 to 20 carbon atoms is preferably an organic group having an ethylenically unsaturated bond. The method for introducing an organic group having an ethylenically unsaturated bond is, for example, reacting a tetracarboxylic dianhydride with an alcohol having an ethylenically unsaturated bond to form a tetracarboxylic diester, and then reacting it with Y ¹ described later. Or an amine compound having a structure of Y ² can be obtained by conducting amidamine condensation polymerization reaction. The same can be obtained when hexacarboxylic acid trianhydride, octacarboxylic acid tetraanhydride, and decacarboxylic pentahydride are used.

The method for producing the aforementioned tetracarboxylic acid diester may also allow the aforementioned acid dianhydride to react with an alcohol in a solvent. From the viewpoint of reactivity, it is preferred to use a reaction activating agent. Examples of the reaction activating agent include tertiary amines such as pyridine, dimethylaminopyridine, and triethylamine. The addition amount of the reaction activating agent is preferably 50 mol% or more and 300 mol% or less, more preferably 100 mol% or more and 150 mol% or less with respect to the tetracarboxylic dianhydride. In addition, a polymerization terminator may be used in a small amount for the purpose of preventing crosslinking of the ethylenically unsaturated bond site during the reaction. Thereby, in the reaction between the alcohol having two or more ethylenically unsaturated bonds having low reactivity and tetracarboxylic dianhydride, heating can be performed within a range of 120 ° C or lower. Examples of the polymerization terminator include phenol compounds such as hydroquinone, 4-methoxyphenol, tert-butylcatechol, and bis-tert-butylhydroxytoluene. The addition amount of the polymerization terminator is preferably 0.1 mol% to 5 mol% with respect to the phenolic hydroxyl group of the polymerization terminator relative to the ethylenically unsaturated bond of the alcohol.

Various methods can be mentioned for the said amidine polycondensation reaction system. For example: a method in which tetracarboxylic acid diester is subjected to ammonium chlorination and then reacted with diamine; a method using a carbonyldiamidine-based dehydration condensing agent; and an activated esterification and then reacted with diamine method.

Examples of the alcohols having an ethylenically unsaturated bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. , 1- (meth) acryloxy-2-propanol, 2- (meth) acrylamine ethanol, methylolketene, 2-hydroxyethylketene, (meth) acrylic acid-2- Hydroxy-3-methoxypropyl, 2-hydroxy-3-butoxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, (methyl) 2-Hydroxy-3-tributoxypropyl acrylate, 2-hydroxy-3-cyclohexylalkoxypropyl (meth) acrylate, 2-hydroxy-3-cyclohexyl (meth) acrylate Alcohols with 1 ethylenically unsaturated bond and hydroxyl group, such as oxypropyl ester, 2- (meth) acryloxyethyl-2-hydroxypropylphthalate; glycerol-1,3-bis (methyl) ) Acrylate, glycerol-1,2-di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Glycerol-1-allyloxy-3-methacrylate, glycerol-1-allyloxy-2-methacrylate, 2-ethyl-2- (hydroxymethyl) propane-1,3- Diyl bis (2-methacrylic acid ), 2-((propenyloxy) -2- (hydroxymethyl) butyl methacrylate, and the like having two or more ethylenically unsaturated bonds and alcohols having one hydroxyl group. "Meth) acrylic acid ester" means methacrylic acid ester or acrylic acid ester. The same applies to similar records. When an acid anhydride is reacted with an alcohol having an ethylenically unsaturated bond, other alcohols may be used. Other alcohols It can be appropriately selected according to various purposes such as adjustment of exposure sensitivity and adjustment of solubility in organic solvents. Specific examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, Aliphatic alcohols such as isobutanol, tertiary butanol, 1-pentanol, 2-pentanol, 3-pentanol, and isopentanol; or ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol mono Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol Monoethyl ether, triethylene glycol monobutyl ether available from alkylene oxide monol like.

In the general formula (1) or (2), Y ¹ and Y ² represent di-, tri-, tetra-, and pentaamine residues, or corresponding isocyanate residues (hereinafter, these are collectively referred to as "amine residues"). In addition, when an amine component or an isocyanate component corresponding to the amine residue is used in the polymerization, these amine residues can be contained in the structural unit. Examples of the amine component system using Y ¹ and Y ² as amine residues are: m-phenylenediamine, p-phenylenediamine, 3,5-diaminobenzoic acid, 1,5-naphthalenediamine, 2 1,6-naphthalenediamine, 9,10-anthracene diamine, 2,7-diaminofluorene, 4,4'-diaminobenzidineaniline, 3,4'-diaminodiphenyl ether, 4 , 4'-diaminodiphenyl ether, 3-co-4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4'-diaminodiphenyl ether, 3,4'-di Amino diphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylhydrazone, 3,4'-diaminodiphenylhydrazone, 4,4'-diamine Diphenylhydrazone, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 4-aminobenzoic acid-4-aminophenyl ester, 9,9-bis ( 4-aminophenyl) fluorene, 1,3-bis (4-aniline) tetramethyldisilazane, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-diethyl-4,4'-diaminobiphenyl, 2,2 ', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3', 4, 4'-tetramethyl-4,4'-diaminobiphenyl, bis (4-aminophenoxyphenyl) fluorene, bis (3-aminophenoxyphenyl) fluorene, bis (4- Aminophenoxy) biphenyl, bis [4- (4 -Aminophenoxy) phenyl] ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy ) Phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-amine (Phenoxy) benzene, 2- (4-aminophenyl) -5-aminobenzo Azole, 2- (3-aminophenyl) -5-aminobenzo Azole, 2- (4-aminophenyl) -6-aminobenzo Azole, 2- (3-aminophenyl) -6-aminobenzo Azole, 1,4-bis (5-amino-2-benzo Azole) benzene, 1,4-bis (6-amino-2-benzo Azole) benzene, 1,3-bis (5-amino-2-benzo Azole) benzene, 1,3-bis (6-amino-2-benzo Azole) benzene, 2,6-bis (4-aminophenyl) benzobis Azole, 2,6-bis (3-aminophenyl) benzobis Azole, bis [(3-aminephenyl) -5-benzo Azole], bis [(4-aminophenyl) -5-benzo Azole], bis [(3-aminephenyl) -6-benzo Azole], bis [(4-aminophenyl) -6-benzo Azole] and other aromatic diamines; bis (3-amino-4-hydroxyphenyl) fluorene, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) ) Hexafluoropropane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl , 4,4'-diamino-6,6'-bis (trifluoromethyl)-[1,1'-biphenyl] -3,3'-diol, 9,9-bis (3-amine Methyl-4-hydroxyphenyl) fluorene, 2,2'-bis [N- (3-aminobenzylmethyl) -3-amino-4-hydroxyphenyl] propane, 2,2'-bis [ N- (3-Aminobenzylidene) -3-amino-4-hydroxyphenyl] hexafluoropropane, 2,2'-bis [N- (4-aminobenzylidene) -3- Amino-4-hydroxyphenyl] propane, 2,2'-bis [N- (4-aminobenzyl) -3-amino-4-hydroxyphenyl] hexafluoropropane, bis [N- (3-Aminobenzylidene) -3-amino-4-hydroxyphenyl] fluorene, bis [N- (4-aminobenzylidene) -3-amino-4-hydroxyphenyl] Hydrazone, 9,9-bis [N- (3-aminobenzylhydrazone) -3-amino-4-hydroxyphenyl] fluorene, 9,9-bis [N- (4-aminobenzylhydrazone) ) -3-amino-4-hydroxyphenyl] fluorene, N, N'-bis (3-aminobenzyl) -2,5-diamino-1,4-dihydroxybenzene, N , N'-Bis (4-aminobenzyl) -2,5-diamino-1,4-dihydroxybenzene, N, N'-bis (4-aminobenzyl) -4 , 4'-diamino-3,3- Hydroxybiphenyl, N, N'-bis (3-aminobenzyl) -3,3'-diamino-4,4-dihydroxybiphenyl, N, N'-bis (4-amino Benzamidine) -3,3'-diamino-4,4-dihydroxybiphenyl and other bisaminophenols; part of the hydrogen atoms of these aromatic rings are alkyl groups with 1 to 10 carbon atoms Compounds substituted with hydrogen, fluoroalkyl, or halogen atoms; and diamines having structures shown below, but are not limited to these. Among these, from the viewpoint of heat resistance, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 4,4'-diaminobiphenyl, 2 , 2'-Dimethyl-4,4'-diaminobiphenyl; From the viewpoint of elongation, preferred are 4,4'-diaminodiphenyl ether, 3-sulfonic acid-4,4 ' -Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamidine, 4,4'-diaminodiphenylsulfide, 4,4'- Diaminodiphenyl ketone. The other diamines to be copolymerized may be used as they are, or the corresponding diisocyanate compound or trimethylsilanized diamine may be used. Moreover, you may use these two or more types of diamine components in combination.

[Chemical 12]

[Chemical 13]

In addition to the aforementioned aromatic diamine, for example, an aliphatic diamine or a diamine having a siloxane structure may be mentioned. Examples of aliphatic diamines include ethylene diamine, 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-cyclohexanedi Amine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis (aminemethyl) cyclohexane, 1,3-bis (aminemethyl) cyclohexane, 1, 4-bis (aminemethyl) cyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine); 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 all trade names, HUNTSMAN (share) system ) And the like, from the viewpoint of further increasing flexibility and enabling high elongation, it is preferable to include an alkylene oxide structure. In addition, by the presence of the ether group, a complex or a hydrogen bond can be formed with the metal, and high adhesion to the metal can be obtained. It may also contain, for example, -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- and the like.

As the diamine having a siloxane structure, bis (3-aminopropyl) tetramethyldisilazane and bis (p-aminophenyl) octamethylpentane are preferred in order to improve adhesion to the substrate. Siloxane.

In addition to the diamine component, for example, (a-1) an amine compound having a trivalent or higher valence. By copolymerizing an amine compound having a trivalence or higher, a branch can be introduced into the main chain. The introduction method refers to a method of introducing a structural unit that becomes m ≧ 1 in the general formula (1), or a method of introducing a structural unit that becomes i ≧ 1 in the general formula (2). The method of using amine component introduction branch is better than the case of using acid component introduction, the former can improve the elastic modulus and elongation according to a high level, so it is better. Although the reason has not been determined, because the solubility of the amine component in the organic solvent is higher than that of the acid component, it is presumed that the branch site generated during the polymerization has a small shift. (a-1) Specific examples of the amine compound having a trivalence or higher include tris (4-aminophenyl) amine, 1,3,5-tris (4-aminophenoxy) benzene, and 1,3 , 5-tris (4-aminophenyl) benzene, 2,4,4'-triamine diphenyl ether, 3,4,4'-triamine diphenyl ether, 2,4,4'-triamine Diphenylhydrazone, 3,4,4'-triaminodiphenylsulfonium, 2,4,4'-triaminodiphenylsulfide, 3,4,4'-triaminodiphenylsulfide, 2 , 4,4'-triaminodiphenyl ketone, 3,4,4'-triaminodiphenyl ketone, tris (4-aminophenyl) methane, 1,1,1-tris (4-amine Phenyl) ethane, 2,4,6-triamino-1,3,5-tri , 2,4,6-tris (4-aminophenoxy) -1,3,5-tris , N ² , N ⁴ , N ⁶ -tris (4-aminophenyl) -1,3,5-tris -2,4,6-triamine, tri (hexylamino) isocyanurate, and triamine, tetraamine, or pentaamine having the following structure, but it is not limited to this.

Among these, from the viewpoints of elastic modulus, elongation, and reaction control during polymerization, triamine compounds are preferred, and triamines having a structure represented by the following general formula (3) are more preferred.

[Chemical 15]

(Z system represents benzene ring, three Rings, aliphatic groups having 1 to 5 carbon atoms, and trivalent organic groups or nitrogen atoms derived from these derivatives. )

Examples of the triamine system having a structure represented by the general formula (3) include tris (4-aminophenyl) amine, 1,3,5-tris (4-aminophenoxy) benzene, and 1,3,5 -Tris (4-aminophenyl) benzene, tris (4-aminophenyl) methane, 1,1,1-tris (4-aminophenyl) ethane, 2,4,6-tris (4-amino) (Phenoxy) -1,3,5-tri And N ² , N ⁴ , N ⁶ -tris (4-aminophenyl) -1,3,5-tris -2,4,6-triamine.

The amine residues of Y ¹ and Y ² can also be introduced using an isocyanate compound. The isocyanate compound can be obtained by reacting a primary amine with triphosgene. The primary amine system can use the amine compounds exemplified for the aforementioned di-, tri-, tetra-, and pentaamine compounds.

The component (A) of the present invention preferably has a weight average molecular weight of 5,000 to 100,000. The weight-average molecular weight is set to 5,000 or more in terms of polystyrene by GPC (gel permeation chromatography), and can improve mechanical properties such as elongation, breaking point strength, and elastic modulus after curing. On the other hand, by setting the weight average molecular weight to 100,000 or less, developability can be improved. In order to obtain mechanical characteristics, more than 20,000. When the component (A) contains two or more kinds of resins, the weight average molecular weight of at least one kind may be within the above range.

Furthermore, in order to show improvement in storage stability and various functions of the photosensitive resin composition of the present invention, the end of the main chain may be blocked with a terminal terminating agent in the component (A). Examples of the terminal terminator include: a monoamine, an acid anhydride, a monocarboxylic acid, a monophosphonium compound, a monoactive ester compound, and the like. In addition, a monoalcohol may be used as a terminal terminator at the later stage of the amidamine polycondensation reaction. Furthermore, by dissolving the resin end with a terminal terminator having a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group, or an allyl group, the dissolution rate of the resin into an alkali solution can be easily achieved. , Exposure sensitivity, and mechanical properties of the obtained cured film are adjusted to a better range.

The introduction ratio of the terminal terminator is preferably 0.1 mol% or more and 60 mol% or less, more preferably 5 mol% or more, in terms of the solubility in the developer and the mechanical characteristics of the obtained cured film. And 50 mol% or less. It is also possible to react a plurality of terminal terminators and introduce a plurality of different terminal groups.

Preferred monoamines used in the terminal terminator are, for example: M-600, M-1000, M-2005, M-2070 (the above are all trade names, manufactured by HUNTSMAN (stock)); aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-amine Naphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-amine Naphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-amine Naphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2- Aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-amine Phenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. These can also be used in two or more types.

The acid anhydride, monocarboxylic acid, monofluorinated chloride compound, and single active ester compound are preferably, for example, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, and the like; 3- Carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto Monocarboxylic acids such as -7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, etc. Monofluorene chloride compounds; for example: terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7- Dicarboxylic naphthalenes, 2,6-dicarboxynaphthalenes, and other dicarboxylic acids are monofluorene chloride compounds in which only one carboxyl group is fluorinated; and monofluorinated chlorine compounds, for example: N-hydroxybenzotriazole, imidazole, N -Hydroxy-5-nor An active ester compound and the like obtained by reacting ene-2,3-dicarboxyamidine. These can also be used in two or more types.

The monoalcohol used for the terminal terminator is exemplified by alcohols that react with the acid anhydride.

In addition, the branched monomer and terminal terminator introduced into the component (A) used in the present invention can be easily detected by the following methods. For example, the resin in which the branched monomer and the terminal terminator have been introduced is dissolved in an acidic solution, decomposed into amine components and acid anhydride components that belong to the structural unit, and then subjected to gas chromatography (GC) and NMR measurement. Easily detect branched monomers or terminal terminators used in the present invention. In addition to GC measurement, external standard materials that do not overlap with the peaks of each component can also be measured. By comparing the integrated value of each peak of the chromatogram with the external standard material, it is also possible to estimate the presence of branched monomers and terminal termination. Mole ratio of each monomer of the agent. In addition, the resin components that have been introduced into the branched monomers and the terminal terminator are directly used in thermal pyrolysis gas chromatography (PGC), infrared spectroscopy, ¹ H-NMR mass spectrometry, ¹³ C-NMR mass spectrometry, and two-dimensional It can be easily detected by NMR mass spectrometry. In this case, the molar ratio of each monomer can be analyzed from the integrated value of infrared spectrum, ¹ H-NMR mass spectrum, or two-dimensional NMR.

The component (A) used in the present invention is preferably polymerized using a solvent. The polymerization solvent is not particularly limited as far as it can dissolve an acid component, an amine component, an alcohol, and a catalyst belonging to the raw material monomer. For example: N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolindione, N, N'-dimethylpropionic urea, N, N-dimethylisobutyric acid ammonium, methoxy-N, N-dimethylpropanamide, and other amines; γ-butyrolactone , Γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone and other cyclic esters; ethyl carbonate, propylene carbonate And other carbonates; diols such as triethylene glycol; phenols such as m-cresol and p-cresol; acetophenone, 1,3-dimethyl-2-imidazolindione, cyclobutane, di Jia Yayu and others.

The photosensitive resin composition system of this invention contains (B) photoinitiator. By containing the (B) photopolymerization initiator, a relief pattern can be formed. (B) The photopolymerization initiator is preferably one that decomposes and / or reacts with light (including ultraviolet rays and electron beams) to cause a radical generator. (B) Photopolymerization initiators that cause decomposition and / or reaction using light to generate free radicals include, for example, 2-methyl- [4- (methylthio) phenyl] -2- Linylpropane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Phenyl-4-yl-phenyl) -butane-1-one, 2-benzyl-2-dimethylamino-1- (4- (Phenylphenyl) -butanone-1, 2,4,6-trimethylbenzylidene phenylphosphine oxide, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide, Bis (2,6-dimethoxybenzylidene)-(2,4,4-trimethylpentyl) -phosphine oxide, 1-phenyl-1,2-propanedione-2- (O -Ethoxycarbonyl) oxime, 1-phenyl-2- (benzylideneoximeimino) -1-acetone, 2-octanedione, 1- [4- (phenylthio) -2- (O -Benzamoxime)], 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1,3-diphenylglycerone-2- (O-ethyl (Oxycarbonyl) oxime, ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamoxime) , 4,4-bis (dimethylamino) diphenyl ketone, 4,4-bis (diethylamino) diphenyl ketone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylamino 2-ethylhexyl benzoate, ethyl p-diethylaminobenzoate, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl Dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy- 2-propyl) ketone, 1-hydroxycyclohexyl phenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, diphenyl Ketones, methyl o-benzylidene benzoate, 4-phenyldiphenyl ketone, 4,4-dichlorodiphenyl ketone, hydroxydiphenyl ketone, 4-benzylidene-4'-formyl Diphenyl sulfide, alkylated diphenyl ketone, 3,3 ', 4,4'-tetrakis (third butylcarbonyl) diphenyl ketone, 4-benzyl-N, N-di Methyl-N- [2- (1-oxy-2-propenyloxy) ethyl] benzenetetramethylammonium bromide, (4-benzylbenzyl) trimethylammonium chloride, 2-hydroxy-3 -(4-benzylidenephenoxy) -N, N, N-trimethyl-1-propene ammonium chloride monohydrate, 2-isopropyloxysulfur 2,4-dimethyloxysulfur 2,4-diethyloxysulfur 2,4-dichlorooxysulfur , 2-hydroxy-3- (3,4-dimethyl-9-oxy-9H-sulfur (-2-yloxy) -N, N, N-trimethyl-1-propaneammonium chloride, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetra Phenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, fluorenone, methylphenyl glyoxylate, η5-cyclopentadienyl-η6-cumyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis (η5-2,4-cyclopentadiene- 1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, oxygen sulfur 2-methyloxysulfur 2-chlorooxysulfur , 4-benzylidene-4-methylphenone, dibenzone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy-2-phenyl-2- Phenylacetophenone, 2-hydroxy-2-methylphenylacetone, p-tert-butyldichloroacetophenone, benzylmethoxyacetal, anthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzoxanthone, dibenzocycloheptanone, methylene anthrone, 4-azidobenzylidene acetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, benzothiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromobenzofluorene, benzamidine peroxide; or photoreducible pigments such as eosin or methylene blue and ascorbic acid or A combination of reducing agents such as triethanolamine. These may contain two or more kinds. In order to further increase the hardness of the cured film, it is preferable to use, for example, an α-amino alkyl phenone compound, a phosphonium oxide phosphine compound, an oxime ester compound, a diphenyl ketone compound with an amino group, or a benzoic acid with an amine group Ester compound.

Examples of the α-amino alkyl phenone compounds are 2-methyl- [4- (methylthio) phenyl] -2- Linylpropane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4- Phenyl-4-yl-phenyl) -butane-1-one or 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone-1. Examples of phosphonium oxide phosphine compounds include: 2,4,6-trimethylbenzylidene phenylphosphine oxide, bis (2,4,6-trimethylbenzylidene) -phenylphosphine oxide or bis (2,6-dimethoxybenzyl)-(2,4,4-trimethylpentyl) -phosphine oxide. Examples of oxime ester compounds include: 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-2- (benzoxime imino)- 1-acetone, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzidine oxime)], 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1,3-diphenylglycerone-2- (O-ethoxycarbonyl) oxime or ethyl ketone, 1- [9-ethyl-6- (2-methyl Benzamidine) -9H-carbazol-3-yl]-, 1- (O-acetamoxime). Examples of the diphenyl ketone compound having an amino group include 4,4-bis (dimethylamino) diphenyl ketone and 4,4-bis (diethylamino) diphenyl ketone. Examples of benzoate compounds with amine groups include: p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid 2-ethylhexyl ester, or p-diethylaminobenzoic acid ethyl ester.

(B) The content of the photopolymerization initiator is 0.5 when the total of the component (A) and the component (C) described later is 100 parts by mass, in order to obtain sufficient sensitivity and suppress outgassing during thermal curing, it is preferably 0.5. At least 20 parts by mass. Among these, more preferably 1.0 mass part or more and 10 mass parts or less.

The photosensitive resin composition of the present invention may contain a sensitizer for the purpose of improving the function of the (B) photopolymerization initiator. By containing a sensitizer, the sensitivity can also be increased and the photosensitive wavelength can be adjusted. Examples of the sensitizer include: Michelin, bis (diethylamino) diphenyl ketone, and diethyloxysulfur. , N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzylidene coumarin, 7-diethylamino-4-methylcoumarin, N- Phenyl However, they are not limited to these.

The photosensitive resin composition of the present invention contains (C) a compound having two or more ethylenically unsaturated bonds (hereinafter also referred to as "(C) component"). By including the component (C), the cross-linking density at the time of exposure can be increased, and the exposure sensitivity can be further improved. In addition, the chemical resistance of the cured film can be further improved. In addition, various molecular functions such as hydrophobicity and elongation can be imparted by further selecting the molecular structure for the purpose of mixing as described later.

(C) The component system may be, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,3-butane Alcohol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,4-butanediol dimethacrylate, 1 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, dimethyloltricyclo Decane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nine (meth) acrylate, tetrapentaerythritol ten (meth) acrylate, pentaerythritol undeca (meth) acrylate, pentaerythritol Quarter Alcohol dodecyl (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl ] 茀, (2- (meth) propenyloxypropoxy) -3-methylphenyl] pyrene or 9,9-bis [4- (2- (meth) propenyloxyoxyethoxy ) -3,5-dimethylphenyl] pyrene, and when it is desired to further increase the exposure sensitivity, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate or Tripentaerythritol octaacrylate; and when it is desired to improve the adhesiveness during development by improving hydrophobicity, dimethylol tricyclodecane diacrylate, dimethylol tricyclodecane dimethacrylate Ester, ethoxylated bisphenol A diacrylate, or 9,9-bis [4- (2-propenyloxyethoxy) phenyl] fluorene; preferably when the elongation of the cured film is to be increased Based on ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate.

The other (C) component compound is, for example, an epoxy (meth) acrylate obtained by reacting a polyfunctional epoxy compound with (meth) acrylic acid. Since epoxy (meth) acrylate can impart hydrophilicity, it can be used for the purpose of improving alkali developability. Examples of the polyfunctional epoxy compound include the following compounds. These polyfunctional epoxy compounds are preferable because they are excellent in heat resistance and chemical resistance.

The molecular weight of the component (C) is preferably 5,000 or less, and more preferably 2,000 or less. If it is 5000 or less, it is preferable because the compatibility with the component (A) can be maintained and the occurrence of whitening of the film can be reduced.

The amount of the component (C) added is preferably 5 parts by mass or more and 100 parts by mass relative to 100 parts by mass of the component (A), and more preferably 10 parts by mass or more and 50 parts by mass or less. If it is in this range, the effect of improving the sensitivity of the exposure and the resistance of the cured film can be easily obtained.

The photosensitive resin composition of the present invention may have (D) an orthocarboxylic acid ester compound (hereinafter also simply referred to as "(D) component"). By containing a (D) component, the storage stability of a photosensitive resin composition can also be improved.

Specific examples of the component (D) include, for example, methyl orthoformate, ethyl orthoformate, isopropyl orthoformate, methyl orthoacetate, ethyl orthoacetate, and isopropyl orthoacetate. Among them, methyl o-formate and ethyl o-formate are preferred from the standpoint of improving the storage stability.

The amount of the component (D) added is preferably 5 parts by mass or more and 1,000 parts by mass or less, more preferably 20 parts by mass or more and 500 parts by mass or less, and 50 parts by mass of the superb part, relative to 100 parts by mass of the component (A). Above 300 parts by mass. If it is in this range, you can easily obtain the improvement of preservation stability.

The photosensitive resin composition of this invention may have (E) antioxidant. By containing the (E) antioxidant, it is possible to suppress the deterioration of mechanical properties such as yellowing of the cured film and elongation during the subsequent heat treatment. In addition, it is preferable to use the antirust effect on the metal material to suppress the oxidation of the metal material.

(E) The antioxidant is preferably a hindered phenol antioxidant or a hindered amine antioxidant. In addition, the number of phenol groups or amine groups in one molecule is preferably 2 or more, and more preferably 4 or more, from the viewpoint that an antioxidant effect can be easily obtained.

Examples of the hindered phenol-based antioxidant system include, but are not limited to, the following structures.

[Chemical 18]

Because hindered phenol compounds inhibit free radical diffusion, they also have the effect of improving resolution. In addition, when development can be performed with an alkaline aqueous solution, it also functions as a dissolution accelerator, and the combination has an effect of suppressing residues.

Examples of hindered amine compounds are: malonate bis (1,2,2,6,6-pentamethyl-4-piperidine) [[3,5-bis (1,1-dimethylethyl) 4-hydroxyphenyl]] methylbutyl ester, bis (1,2,2,6,6-pentamethyl-4-piperidine ester) sebacate, methyl-1,2,2 sebacate , 6,6-pentamethyl-4-piperidinyl ester, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, 2,2,6,6-tetramethyl- 4-piperidine methacrylate, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) sebacate; 1,1-dimethylethyl Product of the reaction of hydrogen peroxide with octane; tetra (1,2,2,6,6-pentamethyl-4-pyridine) butane-1,2,3,4-tetracarboxylic acid ester or tetra ( 2,2,6,6-tetramethyl-4-pyridine) butane-1,2,3,4-tetracarboxylic acid ester.

The amount of the (E) antioxidant added is preferably 0.1 parts by mass or more and 10.0 parts by mass, and more preferably 0.3 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the component (A). When it is in this range, the developability and the effect of suppressing discoloration due to heat treatment can be appropriately maintained.

The photosensitive resin composition of the present invention may have (F) a nitrogen atom-containing heterocyclic compound. By having a heterocyclic compound (F) containing a nitrogen atom, the bottom layer of a metal that is easily oxidized such as copper, aluminum, and silver can obtain high adhesion. Although the mechanism is not clear, it can be speculated that the metal coordination ability of the nitrogen atom is used to interact with the metal surface, and the bulk of the heterocycle is used to stabilize the interaction.

(F) Examples of heterocyclic compounds containing nitrogen atoms include: imidazole, pyrazole, indazolyl, carbazole, pyrazoline, pyrazidine, triazole, tetrazole, pyridine, piperidine, pyrimidine, pyridine ,three , Cyanuric acid, isocyanuric acid, and derivatives thereof.

(F) Heterocyclic compounds containing nitrogen atoms. More examples include: 1H-imidazole, 1H-benzimidazole, 1H-pyrazole, indazole, 9H-carbazole, 1-pyrazoline, 2-pyridine Oxazoline, 3-pyrazoline, pyrazidine, 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole , 5-phenyl-1H-triazole, 4-tert-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxybenzene Triazole, 5-phenyl-1- (2-dimethylaminoethyl) triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5- Bis (α, α-dimethylbenzyl) phenyl] -benzotriazole, 2- (3,5-di-third-butyl-2-hydroxyphenyl) benzotriazole, 2- (3- Tert-butyl-5-methyl-2-hydroxyphenyl) -benzotriazole, 2- (3,5-di-tert-pentyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-Hydroxy-5'-third octylphenyl) benzotriazole, hydroxyphenylbenzotriazole, toltriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H- Benzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H- Azole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazolepyridine, pyridine, 1H-piperidine, dimethylpiperidine, pyrimidine, thymine (thymine), uracil, pyridine , 1,3,5-three , Melamine, 2,4,6-tris (2-pyridine) -1,3,5-tris , 2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-tris , 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-tris , 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-tris 2-yl) -5-hydroxyphenyl, tris ((meth) acryloxyethyl) isocyanurate, tris (glycidyloxyethyl) isotricyanate, and the like. Among these, 1H-benzotriazole, 4-methyl-1H-methylbenzotriazole, 5-methyl-1H are preferred from the viewpoints of ease of synthesis and reactivity with metals. -Methylbenzotriazole, 4-carboxy-1H-benzotriazole, 5-carboxy-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl- 1H-tetrazole and the like.

(F) The addition amount of the nitrogen atom-containing heterocyclic compound is preferably 0.01 parts by mass or more and 5.0 parts by mass or less, more preferably 0.05 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the component (A). If it is in this range, the developability and the stabilization effect of the underlying metal can be appropriately maintained.

The photosensitive resin composition of the present invention may contain a solvent. Examples of the solvent system include: N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N, N-dimethylformamide, N, N- Dimethylacetamide, dimethylarsine, 1,3-dimethyl-2-imidazolindione, N, N'-dimethylpropaneurea, N, N-dimethylisobutyric acid Polar aprotic solvents such as fluorenamine, methoxy-N, N-dimethylpropanamide; tetrahydrofuran, 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, Ester such as 3-methyl-3-methoxybutyl acetate; alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol; toluene, xylene And other aromatic hydrocarbons. These may contain 2 or more types.

The content of the solvent is preferably 100 parts by mass or more relative to 100 parts by mass of the component (A). In order to dissolve the composition, it is preferably 100 parts by mass or more, and it is preferably 1,500 parts by mass to form a coating film having a film thickness of 1 μm or more. The following.

The photosensitive resin composition of the present invention may contain, for example, surfactants; esters such as ethyl lactate and propylene glycol monomethyl ether acetate; alcohols such as ethanol for the purpose of improving the wettability with the substrate as needed. Class; ketones such as cyclohexanone, methyl isobutyl ketone; tetrahydrofuran, two Ethers such as alkane.

In addition, in order to improve the adhesion with the substrate, the photosensitive resin composition of the present invention may contain a silane coupling agent of a silicon component within a range that does not damage and storage stability. Examples of the silane coupling agent system include: trimethoxyaminopropylsilane, trimethoxycyclohexylepoxyethylsilane, trimethoxyvinylsilane, trimethoxythiolpropylsilane, and trimethoxypropyleneoxy Propylsilane, tris (trimethoxysilylpropyl) isocyanurate, triethoxyaminepropylsilane, triethoxycyclohexylepoxyethylsilane, triethoxyvinylsilane , Triethoxythiol propylsilane, triethoxyglycidoxypropylsilane, tris (triethoxysilylpropyl) isotricyanate, and trimethoxyaminepropylsilane ; Or a reactant of triethoxyaminopropylsilane and acid anhydride. This reactant system can be used in a sulfamic acid state or a fluorinated state. Examples of the acid anhydride system to be reacted include: succinic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, pyromellitic dianhydride, 3,3 ', 4,4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyl ketone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dianhydride, 4,4'- Oxydiaphthalic dianhydride. The preferable content of the silane coupling agent is 0.01 to 10 parts by mass based on 100 parts by mass of the component (A).

Next, the shape of the photosensitive resin composition of this invention is demonstrated.

The photosensitive resin composition of the present invention is not limited in shape before being extracted before containing the above-mentioned (A) component, (B) photopolymerization initiator, and (C) component, and may be, for example, a paste or a sheet.

In addition, the photosensitive sheet of the present invention refers to a method in which the photosensitive resin composition of the present invention is coated on a support and dried at a temperature and time within a range in which the solvent can volatilize to obtain a sheet that has not been completely hardened. The material is in a state soluble in an organic solvent or an alkaline aqueous solution.

The support is not particularly limited, and various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used. For the bonding surface of the support and the photosensitive resin composition, in order to improve the adhesion and peelability, surface treatments such as polysiloxane, silane coupling agent, aluminum chelating agent, and polyurea may be performed. The thickness of the support is not particularly limited, but it is preferably in the range of 10 to 100 μm from the viewpoint of workability. Moreover, in order to protect the film surface of the photosensitive composition obtained by coating, a protective film may be provided on the film surface. Thereby, the surface of the photosensitive resin composition can be protected from pollutants such as garbage and fine dust in the atmosphere.

Examples of the method for applying the photosensitive resin composition to a support include spin coating using a spin coater, spray coating, roll coating, screen printing, a knife coater, and a die coater. , Calender coater, meniscus coater, bar coater, roll coater, intermittent roll coater, gravure coater, screen coater, slit die coater and other methods. In addition, the thickness of the coating film varies depending on the coating method, the solid content concentration, and viscosity of the composition. From the viewpoint of coating film uniformity, the film thickness after drying is usually preferably 0.5 μm or more and 100 μm. the following.

For drying, you can use, for example: oven, heating plate, infrared, etc. The drying temperature and the drying time may be within a range where the solvent can be volatilized, and are preferably appropriately set in a range where the photosensitive resin composition is in an uncured or semi-cured state. Specifically, it is preferably performed in the range of 40 ° C to 150 ° C for 1 minute to tens of minutes. In addition, stepwise heating may be performed by combining these temperatures, and for example, heat treatment may be performed at 80 ° C. and 90 ° C. for 2 minutes each.

Next, a method of forming a cured film relief pattern using the photosensitive resin composition or the photosensitive sheet of the present invention will be described.

The photosensitive resin composition of this invention is apply | coated on a board | substrate, or the said photosensitive sheet is laminated | stacked on a board | substrate. The substrate system uses, for example: metal-plated copper substrate, silicon wafer; and the material system uses, for example, ceramics, gallium arsenic, etc., but it is not limited to these. The coating method includes methods such as spin coating using a spin coater, spray coating, and roll coating. In addition, the thickness of the coating film varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like. Generally, the coating is performed so that the film thickness becomes 0.1 to 150 μm after drying.

In order to improve the adhesion between the substrate and the photosensitive resin composition, the substrate may be subjected to a pretreatment using the silane coupling agent. For example, the silane coupling agent is dissolved in 0.5 to 20% by mass in, for example, isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. The surface of the solution in a solvent such as spin coating, dipping, spray coating, or steam treatment. Depending on the situation, a heat treatment at 50 ° C to 300 ° C will be performed afterwards to make the substrate and the silane coupling agent react.

Next, the coated photosensitive resin composition or the substrate on which the photosensitive sheet of the present invention is laminated is dried to obtain a photosensitive resin composition film. It is best to use an oven, a heating plate, infrared rays, etc. for drying for 50 minutes to 150 ° C for 1 minute to several hours. In the case of a photosensitive sheet, a drying step may not be performed.

Next, the photosensitive resin composition film is exposed to actinic rays through a mask having a desired pattern and exposed. The actinic rays used in the exposure are, for example, ultraviolet rays, visible rays, electron beams, X-rays, etc. The present invention preferably uses i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

Second, the exposed photosensitive resin composition film may be subjected to a post-exposure baking (PEB) step, if necessary. The PEB step is preferably performed using, for example, an oven, a heating plate, infrared rays, etc., in a range of 50 ° C to 150 ° C for 1 minute to several hours.

When a resin pattern is formed, the unexposed part is removed using a developing solution after exposure. The developing solution used in the development is preferably a good solvent for the photosensitive resin composition or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition insoluble in an alkaline aqueous solution, a good solvent is preferably, for example, N-methylpyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylacetamidine Amine, cyclopentanone, cyclohexanone, γ-butyrolactone, α-ethytyl-γ-butyrolactone, etc., and the lean solvent is preferably, for example, toluene, xylene, methanol, ethanol, isopropanol, Ethyl lactate, propylene glycol methyl ether acetate and water. When a good solvent and a poor solvent are mixed and used, it is preferable to adjust the ratio of the poor solvent to the good solvent according to the solubility of the polymer in the photosensitive resin composition. Moreover, you may use 2 or more types of each solvent (for example, several types may be used in combination). On the other hand, when the photosensitive resin composition is dissolved in an alkaline aqueous solution, the developing solution used in the development is a solution capable of dissolving and removing soluble polymers in the alkaline aqueous solution, and is typically an alkaline aqueous solution in which an alkali compound has been dissolved. Examples of the basic compound include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, and dimethylamine. , Dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like. In addition, depending on the situation, for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide can be added to the alkaline aqueous solution. Polar solvents such as dimethylarsine, γ-butyrolactone, dimethylpropenamide; alcohols such as methanol, ethanol, isopropanol; esters such as ethyl lactate, propylene glycol monomethyl ether acetate; cyclopentanone , Cyclohexanone, isobutyl ketone, methyl isobutyl ketone and other ketones, etc., these can be added alone or in combination. After development, it is preferable to perform a washing treatment with an organic solvent or water. When an organic solvent is used, in addition to the above-mentioned developing solution, for example, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and the like can also be used. In the case of using water, for example, alcohols such as ethanol and isopropyl alcohol; and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water and then subjected to a cleaning treatment.

After development, a thermal crosslinking reaction is performed at a temperature of 150 ° C to 320 ° C to harden it. This heat treatment can be performed at a selected temperature for stepwise heating or at a certain temperature range for continuous heating for 5 minutes to 5 hours. One example was heat treatment at 130 ° C and 200 ° C for 30 minutes each. The lower limit of the hardening conditions of the present invention is preferably 170 ° C or higher, and in order to sufficiently harden, it is more preferably 180 ° C or higher. The upper limit of the curing conditions is preferably 280 ° C or lower. In particular, since the present invention can provide a cured film having excellent low-temperature curability, the upper limit is more preferably 250 ° C or lower.

The cured film formed by the photosensitive resin composition of the present invention can be used as an insulating film or a protective film constituting an electronic component.

Here, the electronic components are, for example, active components with semiconductors such as transistors, diodes, integrated circuits (ICs), and memories; and passive components such as resistors, capacitors, and inductors. In addition, an electronic component using a semiconductor is also referred to as a "semiconductor device".

Specific examples of hardened films in electronic parts are quite suitable for, for example: passivation films for semiconductors; surface protection films for semiconductor elements, TFTs (Thin Film Transistors, etc.); heavy layers of 2 to 10-layer high-density multilayer wiring Interlayer insulation films such as interlayer insulation films between wirings; insulation films for touch panel displays, protective films, and insulation layers of organic electroluminescence elements are not limited to this, and various structures can be adopted.

Furthermore, the surface of the substrate on which the cured film is formed can be appropriately selected according to the purpose and procedure, and can be, for example, silicon, ceramic, glass, metal, epoxy, etc., or a plurality of these can be arranged on the same surface.

Next, an application example of a semiconductor device having a bump using a cured film cured by the photosensitive resin composition of the present invention and having bumps will be described with reference to the drawings. FIG. 1 is an enlarged sectional view of a pad portion of a semiconductor device having a bump according to the present invention. As shown in FIG. 1, a silicon wafer 1 is formed with a passivation film 3 on an aluminum (2) aluminum pad 2 for input / output (hereinafter referred to as “Al”), and a through hole is formed in the passivation film 3. An insulating film 4 is formed by patterning a hardened film hardened by the photosensitive resin composition of the present invention thereon, and a metal (Cr, Ti, etc.) film 5 is formed by being connected to the Al pad 2, and a metal is formed by electrolytic plating or the like Wiring (Al, Cu, etc.) 6. The metal film 5 etches the periphery of the solder bump 10 to insulate each pad. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. The hardened film of the insulating film 7 hardened by the photosensitive resin composition can be subjected to thick film processing in the cutting line 9.

Furthermore, since the cured film of the present invention is excellent in elongation and elastic modulus, it can also relieve the stress from the end-capping resin during installation, so that damage to the low-k layer can be prevented, and a highly reliable semiconductor device can be provided.

Next, a detailed manufacturing method of the semiconductor device is shown in FIG. 2. As shown in 2a of FIG. 2, an input / output Al pad 2 and a passivation film 3 are formed on a silicon wafer 1, and an insulating film 4 is formed by patterning a cured film hardened with the photosensitive resin composition of the present invention. Next, as shown in 2b of FIG. 2, a metal (Cr, Ti, etc.) film 5 is formed so as to be connected to the Al pad 2, and then as shown in 2c of FIG. 2, a metal wiring 6 is formed by a plating method. Next, as shown in 2d ′ of FIG. 2, the photosensitive resin composition before curing according to the present invention is applied, and the pattern shown in FIG. 2d is formed through an optical lithography step to form an insulating film 7. At this time, the photosensitive resin composition of the insulating film 7 before curing is subjected to thick film processing for the scribe line 9. When forming a multilayer wiring structure with three or more layers, the above steps can be repeated to form each layer.

Next, as shown in 2e and 2f of FIG. 2, a barrier metal 8 and a solder bump 10 are formed. Then, a crystal dicing is performed along the last dicing path 9 to separate each wafer. When the insulating film 7 is not patterned on the scribe line 9, or when residue is left, cracks or the like may occur during dicing, which may affect the reliability evaluation of the wafer. Therefore, according to the present invention, it is possible to provide pattern processing that is excellent in thick film processing, so that high reliability of a semiconductor device can be obtained, which is very good.

The cured film hardened from the photosensitive resin composition and / or the photosensitive sheet of the present invention can form a hollow structure. It is especially suitable for forming hollow structures of micron order. The specific example shown in FIG. 3 is a cross-sectional view of forming a hollow structure on a silicon wafer. FIG. 3 is a cross-sectional view of a state where a first layer (pillar layer) 12 is formed on a silicon wafer 11 and a second layer (roof layer) 13 is formed thereon. FIG. 4 illustrates a method for forming a hollow structure using a plan view. On the silicon wafer 11, a first layer (pillar layer) 12 is formed using a photosensitive resin composition or a photosensitive sheet, and after curing (4a in FIG. 4), a second layer (roof layer) is formed using a photosensitive sheet. ) 13, obtained after hardening (4b of FIG. 4). 4b in FIG. 4 is an example in which the size of the second layer (roof layer) 13 is smaller than that of the first layer (pillar layer) 12. If necessary, the second layer (roof layer) 13 may be formed larger than the first layer (pillar layer) 12 to form an eaves portion. Moreover, via holes, slits, etc. may be formed in the second floor (roof floor) 13. This hollow structure is suitable for electronic parts that require it.

    [Example]    

Hereinafter, the present invention will be described with examples, but the present invention is not limited by these examples. First, the evaluation method of each Example and a comparative example is demonstrated. For the evaluation, a photosensitive resin composition (hereinafter referred to as "varnish") before curing was filtered using a polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) having an average pore diameter of 1 m in advance.

    (1) determination of molecular weight    

(A) The weight-average molecular weight (Mw) of the component was confirmed using a GPC (gel permeation chromatography) device Waters 2690-996 (manufactured by Nihon Waters). The developing solvent was measured using N-methyl-2-pyrrolidone (hereinafter referred to as "NMP"), and the weight average molecular weight (Mw) and the degree of dispersion (PDI = Mw / Mn) were calculated in terms of polystyrene.

    (2) Pattern workability         (2) -1 sensitivity    

The varnish was spin-coated on a silicon wafer using a spin coater (1H-360S, manufactured by MIKASA, Inc.), and then heated using a hot plate (SCW-636, manufactured by Dainippon SCREEN Co., Ltd.) for 3 minutes at 120 ° C Bake and prepare a pre-baking film with a film thickness of 11 μm. A parallel light mask aligner (hereinafter referred to as "PLA") (PLA-501F manufactured by Canon) was used for the obtained pre-baked film, and a super-high-pressure mercury lamp was used as a light source, with a gray scale mask for sensitivity measurement being interposed therebetween. (2 ~ 50μm pattern with lines and space of 1: 1), exposure is performed according to the contact. Then, perform exposure and baking at 120 ° C for 1 minute, and then use the coating and developing device MARK-7. When the polymer is not dissolved in the alkaline aqueous solution, the developing solution is sprayed and developed with cyclopentanone for 2 minutes, and then propylene glycol is used. Monomethyl ether acetate was washed for 30 seconds. When the polymer is dissolved in an alkaline aqueous solution, a 2.38 mass% tetramethylammonium hydroxide (hereinafter referred to as "TMAH") aqueous solution (trade name "ELM-D", manufactured by Mitsubishi Gas Chemical Co., Ltd.) is used as the developing solution for 90 seconds. The stirring and development of the bell was followed by washing with water for 30 seconds.

After development, the film thickness was measured, and the minimum exposure amount at which the residual film ratio of the exposed portion exceeded 90% was set to "sensitivity". The exposure amount was measured with an I-ray illuminance meter.

The film thickness was measured using a Lambda Ace STM-602 manufactured by Dainippon SCREEN Co., Ltd. and the refractive index was 1.629. The same applies to the film thickness described below.

    (2) -2 resolution    

Measure the exposure amount according to the sensitivity defined by (2) -1, and perform the minimum pattern size after development.

    (3) Evaluation of drug resistance    

The varnish was applied on a silicon wafer, and the film thickness was 10 μm after pre-baking at 120 ° C for 3 minutes. The coating was developed using a coating and developing device MARK-7 by a spin coating method. After pre-baking, PLA was used. Exposure to the entire surface of the coating film at 300 mJ / cm ² , and then use an inert furnace CLH-21CD-S under a nitrogen flow and an oxygen concentration of 20 ppm or less, and raise the temperature to 230 ° C. at a heating rate of 3.5 ° C. per minute, and then 230 ° C. Heat treatment was performed for 1 hour. After the temperature dropped below 50 ° C, the silicon wafer was taken out, and the cured film was immersed in an organic chemical solution (dimethylarsine: 25% TMAH aqueous solution = 92: 2) at 40 ° C for 10 minutes. Dissolve. As a result, when the pattern did not peel or dissolve, it was rated as a good "2", and when the pattern was observed to peel or dissolve, it was rated as a bad "1".

    (4) Determination of elongation and elastic modulus    

The varnish was applied on a 6-inch (15.24cm) silicon wafer, and the film thickness was 11 μm after pre-baking at 120 ° C for 3 minutes. The coating was developed using a coating and developing device ACT-8 by spin coating After pre-baking, the entire surface was exposed to 300 mJ / cm ² using PLA, and an inert furnace CLH-21CD-S (manufactured by Koyo Thermo Systems) was used to raise the oxygen concentration to 20 ppm or less and increase the temperature to 3.5 ° C / min. 230 ° C, and then heat-treated at 230 ° C for 1 hour. After the temperature was reduced to below 50 ° C., the silicon wafer was taken out and immersed in 45 mass% hydrofluoric acid for 5 minutes, and the cured film of the resin composition was peeled from the wafer. This film was cut into a thin square shape with a width of 1.5 cm and a length of 9 cm. Using a tension machine RTM-100 (manufactured by ORIENTEC Co., Ltd.), the film was stretched at a speed of 50 mm / ° C at a room temperature of 23.0 ° C and a humidity of 45.0% RH Tensile tests are performed (fixture interval = 2cm), and elongation at break and elastic modulus are measured. The measurement is performed on 10 thin squares per specimen, and the average of the first 5 digits is calculated from the results (significant digits = 2 digits).

    (5) Evaluation of copper substrate adhesion    

Evaluation of adhesion to metallic copper was performed according to the following method.

First, a varnish is applied on a metal-plated copper substrate having a thickness of about 3 μm by a spin coating method, and then a heating plate (D-SPIN manufactured by Dainippon SCREEN Co., Ltd.) is used, and baked at 120 ° C for 3 minutes. Finally, a pre-baking film having a thickness of 8 μm was prepared. The entire surface was exposed to 300 mJ / cm ² using PLA. The film was heated using an inert furnace CLH-21CD-S (manufactured by Koyo Thermo Systems (Koyo)) at an oxygen concentration of 20 ppm or less to 230 ° C. at 3.5 ° C./min. Heat treatment was performed at 230 ° C for 1 hour. When the temperature drops below 50 ° C, the substrate is taken out and the substrate is divided into two parts. For each substrate, a single-sided knife is used to score 10 rows and 10 columns of checkerboard-shaped cuts on the cured film at 2 mm intervals. Using one of the sample substrates, tearing was carried out using "saipan tape" (registered trademark), and the adhesion characteristics between the metal material / resin hardened film were evaluated according to how many checkerboard peeling out of 100 checkerboards. In addition, for another sample substrate, a fracturing test (PCT) device (HAST CHAMBER EHS-211MD, manufactured by Tabai ESPEC) was used to perform PCT treatment at 121 ° C and 2 atmospheres for 400 hours, and then the tearing was performed. Open test. Any of the related substrates were tested in the tear test. The number of peeling is 0, which is rated as a very good "4". The number of peeling is 1 or more, and less than 20 is rated as a good "3". Those with more than 20 peels and less than 50 were rated as acceptable "2", and those with more than 50 peels were rated as "1" as bad.

    (6) Reliability evaluation    

The reliability evaluation was performed according to the following method.

    (6) -1. Evaluation of mechanical characteristics after high temperature storage (HTS)    

On a 6-inch (15.24cm) silicon wafer, the varnish was pre-baked at 120 ° C for 3 minutes, and the film thickness was 11 μm. The coating and development device MARK-7 was used to perform coating and pre-coating by spin coating. After baking, the entire surface was exposed to 300 mJ / cm ² using PLA, and then PLA was used, using an inert furnace CLH-21CD-S (manufactured by Koyo Thermo Systems), at an oxygen concentration of 20 ppm or less, and heating at 3.5 ° C / min. It was heated to 230 ° C and subjected to heat treatment at 230 ° C for 1 hour. After the temperature is lowered below 50 ° C, the substrate is taken out, and then a high-temperature storage tester is used to perform a treatment at 150 ° C for 500 hours. The wafer was taken out, and the elongation and strength were evaluated from the order after the hydrofluoric acid treatment described in "(4) Measurement of elongation and elastic modulus".

    (6) -2. Evaluation of adhesion after high temperature storage (HTS)    

The varnish was spin-coated on a metal-plated copper substrate having a thickness of about 3 μm using a spin coater (manufactured by MIKASA), followed by a hot plate (D-SPIN manufactured by Dainippon SCREEN Co., Ltd.) at 120 The heating plate at ℃ was baked for 3 minutes, and a final pre-baking film with a thickness of 8 μm was produced. The entire surface was exposed to 300 mJ / cm ² using PLA. The film was heated to 220 ° C. at 3.5 ° C./min at an oxygen concentration of 20 ppm or less using an inert furnace CLH-21 CD-S (manufactured by Koyo Thermo Systems). A heat treatment was performed at 220 ° C for 1 hour. When the temperature is lowered below 50 ° C, the substrate is taken out, and a single-sided knife is used to score 10 rows and 10 columns of checkerboard-shaped cuts on the cured film at 2 mm intervals. For such a sample substrate, a high-temperature storage tester was used to perform a heat preservation treatment at 150 ° C. for 500 hours, and then the tear test was performed. Any of the related substrates were tested in the tear test. The number of peeling is 0, which is rated as a very good "4". The number of peeling is 1 or more, and less than 20 is rated as a good "3". Those with more than 20 peels and less than 50 were rated as acceptable "2", and those with more than 50 peels were rated as "1" as bad.

    (7) Preservation stability of varnish    

The adjusted varnish viscosity and the viscosity after 23 weeks at 23 ° C. were measured, and the viscosity change rate before and after the storage was calculated.

The smaller the viscosity change rate before and after standing, the better the storage stability.

    [Synthesis example 1] Synthesis of triacid anhydride (acid-1)    

Under a dry nitrogen stream, 7.1 g (0.033 mol) of 3,4,4'-triaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and 34.2 g (0.3 mol) of allyl glycidyl ether were made. It was dissolved in 100 g of tetrahydrofuran (THF) and cooled to -15 ° C. In this way, 22.1 g (0.11 mol) of trimellitic acid chloride dissolved in THF: 50 g was dropped so that the temperature of the reaction solution did not exceed 0 ° C. After the dropping was completed, a reaction was performed at 0 ° C for 4 hours. This solution was concentrated using a rotary evaporator, thrown into 1 L of toluene, and subjected to fractional filtration and drying to obtain an acid anhydride (acid-1).

    [Synthesis Example 2] Synthesis of Triacid Anhydride (Acid-2)    

Under a dry nitrogen stream, 14.1 g (0.033 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 22.1 g (0.11 mol) of trimellitic acid chloride were dissolved in THF: 150 g, and cooled to 5 ° C. . 11.1 g (0.11 mol) of triethylamine diluted with THF: 50 g was added dropwise so that the temperature of the reaction solution did not exceed 30 ° C. After the dropping was completed, a reaction was performed at room temperature for 4 hours. This solution was filtered to remove the triethylamine hydrochloride. After the filtrate was concentrated by a rotary evaporator, it was thrown into 1 L of toluene, filtered, and dried to obtain an acid anhydride (Acid-2).

    [Synthesis Example 3 Synthesis of Polyimide Precursor (P-1)]    

A 500 ml capacity separable flask was charged with 31.02 g (0.10 mol) of 4,4'-oxydiphthalic dianhydride (ODPA) and 26.03 g of 2-hydroxyethyl methacrylate (HEMA). (0.20 mol) and γ-butyrolactone 76 ml, 16.22 g (0.21 mol) of pyridine was added while stirring at room temperature to obtain a reaction mixture. After the exothermic heat generated by the reaction has ended, it is allowed to cool to room temperature and left for another 16 hours.

Next, a solution of 41.27 g (0.2 mol) of dicyclohexylcarbonyldiimide (DCC) dissolved in 40 mL of γ-butyrolactone was added to the reaction mixture under stirring for 20 minutes under ice-cooling, followed by stirring. While stirring, add 20% of 4,4'-diaminodiphenyl ether (DAE) 17.72g (0.0885mol) and 1,3,5-tris (4-aminophenoxy) benzene (TAPOB) 0.40g over 20 minutes. (0.001 mol) A solution suspended in 100 ml of γ-butyrolactone. After further stirring at room temperature for 2 hours, 6 ml of ethanol (EtOH) was added and stirred for 1 hour, and then 65 mL of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.

The obtained reaction solution was added to 800 ml of ethanol to produce a precipitate composed of a crude polymer. The produced crude polymer was filtered and dissolved in 300 mL of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 6 L of water to precipitate a polymer, and the precipitate was collected by filtration, and then washed three times with water, and then vacuum-dried to obtain a powdery polyimide precursor (P-1 ). The molecular weight of the polyimide precursor (P-1) was measured by a gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 29,000 and PDI was 2.5. The structural unit that becomes the branch point of the main chain in P-1 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 0.9 mol% of the total structural unit.

    [Synthesis Example 4 Synthesis of Polyimide Precursor (P-2)]    

A polyimide precursor P-2 was obtained in the same manner as in Synthesis Example 1 except that the loading amount of DAE was changed to 16.52 g (0.0825 mol) and the loading amount of TAPOB was changed to 2.00 (0.005 mol). The weight average molecular weight (Mw) is 35,000, and the PDI is 3.0. The structural unit that becomes the branch point of the main chain in P-2 calculated by ¹ H- and ¹³ C-two-dimensional NMR accounts for 4.7 mol% of the total structural unit.

    [Synthesis Example 5: Synthesis of polyimide precursor (P-3)]    

A polyimide precursor P-3 was obtained in the same manner as in Synthesis Example 1 except that the loading amount of DAE was changed to 15.02 g (0.075 mol) and the loading amount of TAPOB was changed to 3.99 g (0.010 mol). The weight average molecular weight (Mw) is 45,000, and the PDI is 4.0. The structural unit which becomes the branch point of the main chain in P-3 calculated by ¹ H- and ¹³ C-two-dimensional NMR accounts for 9.5 mol% of the total structural unit.

    [Synthesis Example 6: Synthesis of polyimide precursor (P-4)]    

A polyfluorene imine precursor P-4 was obtained in the same manner as in Synthesis Example 1 except that TAPOB was changed to 0.29 g (0.001 mol) of tris (4-aminophenyl) amine (TAPA). The weight average molecular weight (Mw) is 28,000, and the PDI is 2.8. The structural unit that becomes the branch point of the main chain in P-4 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 0.9 mol% of the total structural unit.

    [Synthesis Example 7: Synthesis of polyimide precursor (P-5)]    

In addition to changing TAPOB to 2,4,6-tris (4-aminophenoxy) -1,3,5-tris (TAPT) Except for 0.40 g (0.001 mol), the polyimide precursor P-5 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) is 26,000, and the PDI is 2.7. The structural unit that becomes the branch point of the main chain in P-5 calculated by ¹ H- and ¹³ C-two-dimensional NMR accounts for 0.9 mol% of the total structural unit.

    [Synthesis Example 8: Synthesis of polyimide precursor (P-6)]    

A polyimide precursor P-6 was obtained in the same manner as in Synthesis Example 1 except that TAPOB was changed to 3,4,4'-triaminodiphenyl ether (TADPE) 0.22 g (0.001 mol). The weight average molecular weight (Mw) is 27,000, and the PDI is 2.7. The structural unit that becomes the branch point of the main chain in P-6 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 0.9 mol% of the total structural unit.

    [Synthesis Example 9 Synthesis of Polyimide Precursor (P-7)]    

Except changing the ODPA to ODPA: a mixture of 30.55 g (0.0985 mol) and 0.74 g (0.001 mol) of "Acid-1" synthesized in Synthesis Example 1, and changing the DAE loading amount to 18.02 g (0.09 mol), and Except that TAPOB was used, the polyimide precursor P-7 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) is 35,000, and the PDI is 2.9. The structural unit that becomes the branch point of the main chain in P-7 calculated by ¹ H- and ¹³ C-two-dimensional NMR accounts for 0.9 mol% of the total structural unit.

    [Synthesis Example 10 Synthesis of polyimide precursor (P-8)]    

Except changing ODPA to ODPA: a mixture of 30.55 g (0.0985 mol) and "Acid-2" synthesized in Synthesis Example 2 0.95 g (0.001 mol), and changing the DAE loading amount to 18.02 g (0.09 mol), and Except for using TAPOB, the polyimide precursor P-8 was obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) is 27,000, and the PDI is 2.7. The structural unit that becomes the branch point of the main chain in P-8 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 0.9 mol% of the total structural unit.

    [Synthesis Example 11 Synthesis of Polyfluorene (P-9)]    

Except that ODPA was changed to a mixture of ODPA: 30.55 g (0.0985 mol) and 0.95 g (0.001 mol) of "Acid-2" synthesized in Synthesis Example 2, the rest were obtained in the same manner as in Synthesis Example 1. Amine precursor P-9. The weight average molecular weight (Mw) is 27,000, and the PDI is 2.7. The structural unit that becomes the branch point of the main chain in P-9 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 1.8 mol% of the total structural unit.

    [Synthesis Example 12: Synthesis of polyimide precursor (P-10)]    

Except that DAE was changed to 32.39 g (0.0885 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF), polyimide was obtained in the same manner as in Synthesis Example 1. Precursor P-10. P-10 is a polyimide precursor dissolved in an alkaline aqueous solution. The weight average molecular weight (Mw) is 29,000, and the PDI is 2.5. The structural unit that becomes the branch point of the main chain in P-10 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 0.9 mol% of the total structural unit.

    [Synthesis Example 13 Synthesis of Polyfluorene (P-11)]    

Under a dry nitrogen stream, BAHF: 30.56 g (0.0835 mol), TAPOB: 0.4 g (0.001 mol), 1,3-bis (3-aminopropyl) tetramethyldisilaxane (SiDA) 1.24 g (0.005 mol) and 2.18 g (0.02 mol) of 3-aminophenol (MAP) (manufactured by Tokyo Chemical Industry Co., Ltd.) and a terminator, dissolved in NMP: 100 g. ODPA: 31.02 g (0.1 mol) and NMP: 30 g were added thereto, and the reaction was performed at 20 ° C. for 1 hour, and then the reaction was performed at 50 ° C. for 4 hours. Then, it stirred at 180 degreeC for 5 hours. After the stirring was completed, the solution was thrown into 3 L of water and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried with a 50 ° C ventilated dryer for three days to obtain a powdery polyimide (P-11). The weight average molecular weight (Mw) is 26,000, and the PDI is 2.6. P-11 is a polyimide dissolved in an alkaline aqueous solution. The fluorene imidization ratio (fluorene imine ring closure ratio) of P-11 was measured by a known method described below, and it was 100%. The structural unit that becomes the branch point of the main chain in P-11 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 0.9 mol% of the total structural unit.

    <Determination of Imidization Rate>    

The fluorene imidization ratio (R _IM (%)) can be easily obtained by the following method. First, the infrared absorption spectrum of the polymer was measured, it was confirmed by the absorption peaks of polyimide (PEI) derived from the configuration (near 1780 cm ^-1, near 1377 cm ^-1) system exists, and obtains the peak intensity nearby 1377 cm ^-1 (X). Next, this polymer was heat-treated at 350 ° C. for 1 hour, and an infrared absorption spectrum was measured to obtain a peak intensity (Y) near 1377 cm ⁻¹ . The peak intensity ratio is the content of the fluorene imino group in the polymer before the heat treatment, which is equivalent to the ratio of fluorene imine (R _IM = X / Y × 100 (%)).

    [Synthesis Example 14 Synthesis of Polyhydroxysamine (P-12)]    

Under a stream of dry nitrogen, BAHF: 34.25 g (0.0935 mol) and TAPOB: 0.4 g (0.001 mol) were dissolved in NMP: 210 g. 32.25 g (0.09 mol) of 1,1 '-(4,4'-oxybenzyl) diimidazole (PBOM) and 20 g of NMP were added thereto, and the reaction was performed at 85 ° C for 3 hours. Next, SiDA: 1.24 g (0.0050 mol) and NMP: 10 g were added, and the reaction was performed at 85 ° C. for 1 hour. Added as 5-terminated terminator 3.28 g (0.02 mol) of ene-2,3-dicarboxylic anhydride (NA) and NMP: 10 g were reacted at 85 ° C for 30 minutes. After the reaction was completed, it was cooled to room temperature, and acetic acid (54.02 g, 0.90 mol) and NMP were added: 50 g, and the mixture was stirred at room temperature for 1 hour. After the stirring was completed, the solution was thrown into 3 L of water, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and then dried with a 50 ° C. ventilated dryer for three days to obtain a powder of polyhydroxyamidine (P-12). The weight average molecular weight is 40,000, and the PDI is 2.2. The structural unit that becomes the branch point of the main chain in P-12 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 0.9 mol% of the total structural unit.

    [Synthesis Example 15: Synthesis of polyimide precursor (P-13)]    

A polyimide precursor P-13 was obtained in the same manner as in Synthesis Example 1 except that the loading amount of DAE was changed to 10.01 g (0.05 mol) and the loading amount of TAPOB was changed to 7.99 g (0.02 mol). The weight average molecular weight (Mw) was 55,000, and the PDI was 5.0. The structural unit that becomes the branch point of the main chain in P-13 calculated by ¹ H- and ¹³ C-secondary NMR accounts for 18.2 mol% of the total structural unit.

    [Synthesis Example 16 Synthesis of Polyimide Precursor (P-14)]    

A polyimide precursor P-14 was obtained in the same manner as in Synthesis Example 1 except that the loading amount of DAE was changed to 18.02 g (0.09 mol) and TAPOB was not added. The weight average molecular weight (Mw) is 25,000, and the PDI is 2.2.

    [Synthesis Example 17 Synthesis of Polyfluorene (P-15)]    

A polyimide P-15 was obtained in the same manner as in Synthesis Example 13 except that the filling amount of BAHF was changed to 31.11 g (0.085 mol) and TAPOB was not added. The weight average molecular weight (Mw) is 25,000, and the PDI is 2.2.

    [Synthesis Example 18 Synthesis of Polyhydroxysamine (P-16)]    

Except that the filling amount of BAHF was changed to 34.79 g (0.095 mol) and TAPOB was not added, polyhydroxyamidamine P-16 was obtained in the same manner as in Synthesis Example 14. The weight average molecular weight (Mw) is 35,000, and the PDI is 2.4.

    [Synthesis Example 19: Synthesis of polyimide precursor (P-17)]    

A polyimide precursor P-17 was obtained in the same manner as in Synthesis Example 1 except that the loading amount of DAE was changed to 14.42 g (0.072 mol) and the loading amount of TAPOB was changed to 4.27 (0.012 mol). The weight average molecular weight (Mw) is 40,000, and the PDI is 4.2. The structural unit that becomes the branching point of the main chain in P-17 calculated by ¹ H- and ¹³ C-two-dimensional NMR accounts for 11.5 mol% of the total structural unit.

The components (mol ratio) of Synthesis Examples 3 to 19 are shown in Table 1.

    [Example 1]    

Under a yellow light, 10.00 g of polyimide precursor (P-1), 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzidine oxime)] ("IRGACURE OXE-01 (trade name)" made by BASF) (OXE-01) 0.50 g, NK ester 4G (trade name) (made by Shin Nakamura Chemical Industry Co., Ltd., chemical name: tetraethylene glycol dimethacrylic acid Ester) (4G) 2.00g, N-phenyldiethanolamine 1.00g and 3-trimethoxysilyl phthalocyanine 0.30g, dissolved in 15.15g of N-methylpyrrolidone (NMP) and ethyl lactate ( EL) To 3.81 g, add 0.10 g of a 1% by mass EL solution of "Poly Flow 77 (trade name)" (manufactured by Kyoeisha Chemical Co., Ltd.) (Poly Flow 77), which is an acrylic surfactant, and stir to Get varnish. The characteristics of the obtained varnish were measured according to the above-mentioned evaluation method.

    [Example 2]    

Except having changed the polyfluorene imide precursor (P-1) into the polyfluorene imine precursor (P-2), it carried out similarly to Example 1, and implemented.

    [Example 3]    

Except having changed the polyfluorene imine precursor (P-1) into the polyfluorene imine precursor (P-3), it carried out similarly to Example 1, and implemented.

    [Example 4]    

Except having changed the polyfluorene imide precursor (P-1) into the polyfluorene imine precursor (P-4), it carried out similarly to Example 1, and implemented.

    [Example 5]    

Except having changed the polyfluorene imide precursor (P-1) into the polyfluorene imine precursor (P-5), it carried out similarly to Example 1, and implemented.

    [Example 6]    

Except having changed the polyfluorene imine precursor (P-1) into the polyfluorene imine precursor (P-6), it carried out similarly to Example 1, and implemented.

    [Example 7]    

Except having changed the polyfluorene imide precursor (P-1) into the polyfluorene imine precursor (P-7), it carried out similarly to Example 1, and implemented.

    [Example 8]    

Except having changed the polyfluorene imide precursor (P-1) into the polyfluorene imide precursor (P-8), it carried out similarly to Example 1, and implemented.

    [Example 9]    

Except having changed the polyfluorene imide precursor (P-1) into the polyfluorene imine precursor (P-9), it carried out similarly to Example 1, and implemented.

    [Example 10]    

A polyimide precursor (P-1) was changed to a polyimide precursor (P-10), and N-phenyldiethanolamine was not added.

    [Example 11]    

Under yellow light, 10.00 g of polyimide (P-11), OXE-01: 0.50 g, Light Acrylate DCP-A (trade name) (manufactured by Kyoeisha Chemical Co., Ltd., chemical name: dicyclopentane Diene diacrylate) 2.00 g, Light Acrylate BP-6EM (trade name) (manufactured by Kyoeisha Chemical Co., Ltd., chemical name: ethylene oxide adduct of bisphenol A diacrylate) (BP-6EM ) 2.00 g and 0.30 g of vinyltrimethoxysilane were dissolved in NMP: 16.25 g and EL: 4.08 g, 0.10 g of a 1% by mass EL solution of Poly Flow 77 was added, and a varnish was obtained by stirring. The characteristics of the obtained varnish were measured according to the above-mentioned evaluation method.

    [Example 12]    

The procedure was carried out in the same manner as in Example 11 except that the polyamidine (P-11) was changed to the polyhydroxyamidine (P-12).

    [Example 13]    

Except that 0.3 g of a hindered phenol compound IRGANOX245 (trade name) (manufactured by BASF) (IRGANOX245) was further added, the same procedure was performed as in Example 1.

    [Example 14]    

The procedure was carried out in the same manner as in Example 1 except that 0.02 g of 5-methyl-1H-benzotriazole was further added.

    [Example 15]    

Except adding IRGANOX245: 0.3g and 5-methyl-1H-benzotriazole 0.02g, it carried out similarly to Example 1, and implemented.

    [Example 16]    

The procedure was carried out in the same manner as in Example 1 except that 2.0 g of ethyl o-formate was further added.

    [Example 17]    

Except having changed the polyfluorene imide precursor (P-1) into the polyfluorene imine precursor (P-17), it carried out similarly to Example 1, and implemented.

    [Comparative Example 1]    

Except having changed the polyfluorene imide precursor (P-1) into the polyfluorene imine precursor (P-13), it carried out similarly to Example 1, and implemented. However, due to poor development, the correlation sensitivity and resolution were not evaluated.

    [Comparative Example 2]    

Except having changed the polyfluorene imine precursor (P-1) into the polyfluorene imine precursor (P-14), it carried out similarly to Example 1, and implemented it.

    [Comparative Example 3]    

The procedure was carried out in the same manner as in Example 11 except that the polyfluorene imine (P-11) was changed to the polyfluorene (P-15).

    [Comparative Example 4]    

A polyimide (P-11) was changed to polyhydroxyamido (P-16) except that the procedure was carried out in the same manner as in Example 11.

The results of Examples 1 to 15 and Comparative Examples 1 to 4 are shown in Tables 2 and 3.

Claims (14)

A photosensitive resin composition comprising: (A) polyfluorene and polybenzo with a branch from a main chain Among the azoles and these precursors, one or more resins, (B) a photopolymerization initiator, and (C) a compound having two or more ethylenically unsaturated bonds are selected; among them, the main chain in the (A) resin The structural unit of the branch point is a ratio of 0.05 mol% to 12 mol% in the total structural unit. For example, the photosensitive resin composition of claim 1, wherein the structural unit that becomes the branch point of the main chain of the resin (A) contains a structure selected from at least one of the following general formulae (1) and (2) unit; (In the formula, X ¹ represents a divalent to 16-valent organic group having two or more carbon atoms; Y ¹ represents a divalent to 14-valent organic group having two or more carbon atoms; R ¹ and R ² are Represents each independent hydrogen or any of the organic groups having 1 to 20 carbon atoms; p, q, and s represent independent integers of 0 to 4; r represents an integer of 0 to 6; l and m represent Represents the number of branches in the main chain, each independently representing an integer from 0 to 4; among them, l + m ≧ 1; Also, regarding l, m, p, q, r, and s, when the value is 0, the functions in parentheses The radicals respectively represent hydrogen atoms); (In the formula, X ² represents a 4- to 16-valent organic group having 2 or more carbon atoms; Y ² represents a 2- to 10-valent organic group having 2 or more carbon atoms; R ³ and R ⁴ are Represents any one of independent hydroxyl groups or organic groups having 1 to 20 carbon atoms; t and u represent independent integers of 0 to 4; h and i represent branch numbers of the main chain and each independently represents 0 to An integer of 4; h + i ≧ 1; and for h, i, t, and u, when the value is 0, the functional groups in parentheses represent hydrogen atoms, respectively).     The photosensitive resin composition according to claim 1 or 2, wherein the structural unit serving as the branching point of the main chain of the resin (A) contains the structural unit (a-1) derived from an amine compound having a trivalent or higher valence.     The photosensitive resin composition according to any one of claims 1 to 3, wherein the structural unit serving as the branching point of the main chain of the resin (A) contains a structural unit derived from a triamine represented by the general formula (3) ; (Z system represents benzene ring, three A ring, an aliphatic group having 1 to 5 carbon atoms, and a trivalent organic group derived from these derivatives, or a nitrogen atom).     The photosensitive resin composition according to any one of claims 1 to 4, further comprising (D) an o-carboxylic acid ester compound.         The photosensitive resin composition according to any one of claims 1 to 5, further comprising (E) an antioxidant.         The photosensitive resin composition according to any one of claims 1 to 6, further comprising (F) a heterocyclic compound containing a nitrogen atom.         A photosensitive sheet comprising the photosensitive resin composition according to any one of claims 1 to 7.         A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 7 or the photosensitive sheet according to claim 8.         A method for producing a cured film, which is a method for producing a cured film using the photosensitive resin composition according to any one of claims 1 to 7 or the photosensitive sheet according to claim 8; comprising: A step of applying a resin composition on a substrate, or laminating the above-mentioned photosensitive sheet on a substrate, and drying to form a photosensitive resin film; performing a step of exposing the above-mentioned photosensitive resin film; A step of applying a heat treatment to the photosensitive resin film; a step of developing the photosensitive resin film after the heat treatment; and a step of applying a heat treatment to the photosensitive resin film after the development.         A hollow structure having a cured film according to claim 9.         An electronic component having the hollow structure of claim 11.         An electronic part is a relief pattern layer having a hardened film of claim 9.         An electronic component in which the cured film of claim 9 is arranged as an interlayer insulating film between redistribution lines.