TW201211686A - Photosensitive resin composition, fabrication method of cured relief pattern and semiconductor device - Google Patents

Abstract

The invention provides a kind of photosensitive resin composition that will not cause cured film color change on copper or copper alloy, fabrication method of cured relief pattern using the photosensitive resin composition and semiconductor device. The invented photosensitive resin compound is comprised of 100% mass of (A) at least one resin selected from the group consisting of polyamide acid, polyamide acid ester, as precursor for polyimide, polyhydroxy amid, polyamino amide, polyamide, polyamide imide, polyimide, polybenzoazoles, polybenzimidazole, polybenzothiazole, as precursor for polyazole; 0.01 to 10% mass of (B) purine derivative with 100% mass of resin (A) as the basis; and 1 to 50% mass of (C) photosensitive agent with 100% mass of resin (A) as the basis.

Description

201211686 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a photosensitive material for forming an insulating material such as an electronic component, and a convex pattern of a passivation film, a buffer film, and an interlayer insulating film in a semiconductor device. The resin composition 'is a method of producing a cured bump pattern thereof, and a semiconductor device. [Prior Art] Conventionally, an insulating material for an electronic component, a passivation film for a semiconductor device, a surface protective film, an interlayer insulating film, or the like is a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties. Among the polyimine resins, those supplied in the form of photosensitive polyimide precursors can be easily coated, exposed, developed, and cured by heat imidization of the precursor. A heat-resistant convex pattern film is formed. Such a photosensitive polyimide precursor has a characteristic that the step can be greatly shortened compared to the prior non-photosensitive polyimide. On the other hand, in recent years, the method of mounting a semiconductor device on a printed wiring board has changed from the viewpoint of improvement in integration and function, and reduction in wafer size. From the previous installation method using metal pins and erbium tin eutectic soldering, it has gradually changed to BGA (Ball Grid Array) and CSP (Chip Scale) for women who can achieve higher density.

A polyimine film such as Package 'wafer size package is directly in contact with the structure of the solder bump. When such a bump structure is formed, high thermal and chemical resistance is required for the film. It is disclosed that by adding a thermal crosslinking agent to a composition containing a polyimide precursor or a polybenzoxazole precursor, the poly 157416.doc 201211686 yttrium imide film or polybenzo, azole film is improved. A method of heat resistance (refer to Patent Document 1). Further, due to the development of the miniaturization of the semiconductor device, the wiring resistance of the semiconductor device cannot be gradually ignored. Therefore, it is being converted from the wiring of gold or aluminum used so far to the wiring of copper or steel alloy having a lower electric resistance. However, in the conventional photosensitive resin composition, since the compound in the composition easily reacts with copper or a copper alloy, there is a problem that copper or a copper alloy is discolored. As a means for solving the above problems, a method of suppressing discoloration and corrosion by copper or a copper alloy by adding a triazole or a derivative thereof to a composition containing a polyimide precursor (see Patent Document 2) is disclosed. . Further, a method of providing copper with good adhesion to polyimine by introducing an unsaturated heterocyclic group or the like at the terminal of the polyimine (see Patent Document 3) is disclosed (Patent Document 3) [Patent Document] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The problem to be solved] However, the composition disclosed in Patent Document 2 has a problem that discoloration occurs in copper or a copper alloy if the film thickness is increased. Accordingly, an object of the present invention is to provide a 157416.doc 201211686 photosensitive resin composition which can be provided on a copper or copper alloy without causing discoloration, and a hardened smear pattern in which a pattern is formed using the photosensitive resin composition. Manufacturing method and semiconductor device. [Means for Solving the Problems] The present inventors have found that a photosensitive resin composition capable of providing a cured film excellent in discoloration inhibition on copper or a copper alloy by obtaining a noise derivative in the photosensitive resin composition, Thus, the present invention has been completed. That is, the present invention is as follows. [1] A photosensitive resin composition comprising: (Α) selected from the group consisting of polylysine as a polyimide precursor, poly-glycolic acid vinegar, polyhydroxyguanamine which can be a polycarbazole precursor, At least one of a group consisting of polyamine amide, polyamidamine, polyamidimide 'polyimine, polybenzoxazole, polybenzimidazole, and polybenzothiazole: 1 (Β) anthracene derivative: 0.01 to 10 parts by mass based on 1 part by mass of the resin; and (C) sensitizer: based on 1 part by mass of the (a) resin , for 丨 ~ 5 〇 mass parts. [2] The photosensitive resin composition according to [1], wherein the (A) resin is selected from the group consisting of the following formula (1): [Chemical Formula 1]

157416.doc 201211686 U, XA4 valence organic group, Y々2 valence organic group, ηβ2~ι5〇 integer ' and 1 and 112 are each independently a hydrogen atom, or the following general formula (7): [Chemical 2]. R4, R5 0

II (2) -cc=c r3 (wherein R3, R4 and Rs are each independently a hydrogen atom or an organic group having a carbon number of 丨~3, and an integer thereof), or a carbon number A polyimine precursor having a structure represented by a saturated aliphatic group, having the following general formula (3): [Chemical 3]

Η Η IIN—Y2—N —— NH I R6 J Π2 (3) {wherein X2 is a trivalent organic group having a carbon number of 6 to 15, and Y2 is a divalent organic group having a carbon number of 6 to 35, and may be The same structure 'may have a plurality of structures, the rule 6 is an organic group having at least one radical polymerizable unsaturated bond group having a carbon number of 3 to 20, and the enthalpy is an integer of 1 to 1 }} The polyamine of the structure has the following formula (4): [Chemical 4] 0H CO X3 CONH-Y3-NH- -CO-X4-CONH-Y4-NH-OH 〇3 157416.doc • 6 · ( 4) 201211686 {wherein, Y3 is a tetravalent organic group having a carbon atom, and Υ4, Χ3, and \ are each independently a divalent organic group having two or more carbon atoms, ^ is an integer of hiooo, and 114 is 0 to 500. Integer, n3/(n3+n4)>〇5, and there are no restrictions on the order of the three dihydroxydiamine units containing & and Y3 and the units containing \ and \'s diammonium amine} _ The polycarbazole precursor of the structure shown, and having the following general formula (5): [Chemical 5] ολχ5£〇人丫ο /__\ Y5· m3 Π5 {wherein, X5 represents a 4 to 14-valent organic group, Γ5 represents a 2 to 12-valent organic group, and R8 is independently represented by At least one organic group selected from the group consisting of (iv) a thiol group, a ns of an integer of 3 to 2 Å, and an integer of 0 to 10; At least one resin of the group consisting of imines. [3] The photosensitive resin composition according to [1] or [2], wherein the above (8) 嘌呤j organism is selected from the following formula (6): [Chem. 6]

(6)

.NH >/ R9, 'N,刈{wherein 'r9 is a hydrogen atom+, a hydroxyl atom, a hydroxyl group, an amine group or an alkyl group or an aromatic group of carbon number (7), and R10 is a hydrogen atom, a dentate 157416.doc 201211686 · A compound having a carbon number of 1 to 6 alkoxy group, a trans group, a carbyl group or an amine group which may be substituted by a decyl group or an aromatic group having 1 to 1 carbon number, General formula (7): [Chemical 7] Ο

^13 (7) wherein Rn is a hydrogen atom, a halogen atom, a trans group, an amine group or a carbon or a carboxyl group having 1 to 10 carbon atoms, and Rl2 and Rl3 are independently a nitrogen atom, a hydroxyl group or a hydroxy alkane. a compound represented by an alkyl group or an aromatic group having 1 to 10 carbon atoms, and the following general formula (8): [Chemical 8]

In the formula, R14 is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or an alkyl group or an aromatic group having 1 to 10 carbon atoms, and Ri5 is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group. a compound represented by a hydroxyalkyl group or an amine group which may be substituted with an alkyl group or an aromatic group having 1 to 10 carbon atoms, and the following general formula (9): 157416.doc 201211686

Ν Ο) {wherein, Rie is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or an alkyl group or an aromatic group having 1 to 10 carbon atoms, and each independently represents a hydrogen atom, a hydroxyl group, a hydroxyalkyl group or a carbon number At least one anthracene derivative of the group consisting of the compound represented by the alkyl group or the aromatic group (7). [4] The photosensitive resin composition according to any one of [1] to [3] wherein the (B) anthracene derivative is selected from the group consisting of the following formula (1〇):

In the formula, Rl9 is a hydrogen atom, a dentate atom, a trans group, an amine group or a compound having an alkyl group or an aromatic group of carbon number 1, and the following formula (丨1): [Chem. 11]

Han 2 () is a compound represented by a nitrogen atom, a base group or a condensate having a carbon number of 1 to 10, and the following formula (12): 157416.doc •9· 201211686 [Chem. 12]

NH >

, wherein RZ1 is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or a compound having a carbon number of 1 to 10 or an aromatic group, and the following formula (13):

N〇2 八 In the formula, R22 is at least one anthracene derivative of a group consisting of a compound represented by a hydrogen atom, a hydroxyalkyl group or an alkyl group having a carbon number of 丨~1〇. [5] The photosensitive resin composition according to any one of [1] to [3] wherein the (B) anthracene derivative is a compound selected from the group consisting of the above formula (12), and the above formula (13) At least one anthracene derivative of the group consisting of the compounds shown. [6] The photosensitive resin composition according to any one of [1] to [5] further comprising (D) a crosslinking agent: 〇5 to 2 为 based on 100 parts by mass of the above (A) resin Parts by mass. [7] The photosensitive resin composition according to any one of [1] to [6] further comprising (E) an organic titanium compound: 0.05 based on the mass of the (A) resin ~10 parts by mass. [1] The photosensitive resin composition of [7], wherein the (E) organotitanium compound is selected from the group consisting of a titanium chelate compound, a tetraalkoxy titanium compound, and a titanocene compound. At least one compound in the group. [9] (1) A method of producing a hardened convex pattern, comprising: applying a photosensitive resin composition according to any one of [1] to [8] above on a substrate a step of forming a photosensitive resin layer; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a raised pattern; and (4) by The step of heat-treating to form a hardened convex pattern. The method of m is such that the substrate is formed of copper or a copper alloy. The semiconductor device is provided by the above [ 9] or the hardened convex pattern obtained by the method of (10). [Effects of the Invention] According to the present invention, 'by the photosensitive resin composition, the (four) oxime derivative = obtained can be provided on copper or a copper alloy. A cured film of discoloration: a sensible=fat composition, a method for producing a cured projection pattern using the photosensitive resin composition Γ pattern, and a semiconductor package. The present invention will be specifically described below. Symbol table factory, 'through the description of the situation The structure of the open 彡# i does not exist in the molecule, and may be the same or different from each other. 157416.doc -II. 201211686 <Photosensitive resin composition> This month is selected by (A) Free polyamine as a precursor of polyimine, poly-aramidic acid vinegar, polyhydroxy guanamine, polyamine amide, polyamine, polyamidimide, which can be a precursor of poly azole At least one resin of the group consisting of polyimine, polybenzoxazole, polybenzazole, polybenzothiazole: 100 parts by mass; (B) anthracene derivative: (A) resin 1〇〇 The mass fraction is 〇.01 to 10 parts by mass; (C) the sensitizer: 1 to 50 parts by mass based on 100 parts by mass of the (A) resin as an essential component. (A) Resin The (A) resin used in the present invention will be described. The (A) resin of the present invention is selected from the group consisting of polylysine as a polyimine precursor, polyphosphonium amide, polyhydroxyguanamine which can be a poly-, azole precursor, polyamine amide , at least one of a group consisting of polyamine, polyamidimide, polyimine, polybenzoxazole, polybenzopyrazole, polybenzothiazole as a main tool, The s stomach main component means that the resin is contained in an amount of 6 〇 mass/〇 or more of the total resin, and preferably contains 8% by mass or more. Also, if necessary, other resins may be included. The weight average molecular weight of the resins is preferably 1, 1 or more, more preferably 1 or more, from the viewpoint of heat resistance and mechanical properties after heat treatment, in terms of polystyrene conversion by gel permeation chromatography. 5 or more. The upper limit is preferably 1 Torr, and 〇〇〇 is more preferably 50,000 or less from the viewpoint of solubility in the developer in the case of producing a photosensitive resin composition. In the present invention, in order to form a convex pattern, the (A) resin is preferably a photosensitive resin. The photosensitive resin is a resin which is used together with the (c) sensitizer described below to form a photosensitive resin composition of 157416.doc 201211686, which causes dissolution or unsolvation in the subsequent development step. As a photosensitive resin, polylysine as a polyamidene precursor, polyphthalate, polyhydroxyguanamine, polyamine amide, polyamine, polyamidamine which can be a polyazole precursor Among the imine, polyimine, polybenzoxazole, polybenzimidazole, and polybenzothiazole, the resin after heat treatment preferably uses a polyimide precursor in terms of heat resistance and mechanical properties. Polyamide, polyphenyl #salt precursor, polyimine. x These photosensitive resins can be selected in accordance with the following (c) sensitizer to prepare a negative or positive photosensitive resin composition, etc., depending on the intended use. [Polyimide precursor] In the photosensitive resin composition of the present invention, an example of the resin (A) which is optimal in terms of heat resistance and photosensitivity is the above formula (1): One c=o Io R1

HINI Y1ΐ & Η-Ν οI IOMC c=o (1) {In the formula, 乂丨 is a 4-valent organic group, ¥] is a 2-valent organic group, which is a number of 2 to 15 ,, and the heart and the ruler 2 are independent. Is a hydrogen atom, or the above formula: [Chem. 15]

I574l6.doc -13· 201211686 (in the formula, R3, R4 and R_5 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms, and is an integer of 2 to 10), or a carbon group. Polyimine precursors of the structure shown in the number 1 to 4 of saturated aliphatic groups}. The polyimine precursor is converted to polyimine by cyclization by heating (e.g., above 200 ° C). The polyimine precursor is preferably used as a negative photosensitive resin composition. In the above formula (1), the tetravalent organic group represented by Χι is preferably an organic group having a carbon number of 6 to 40, and more preferably -COOR, in terms of both heat resistance and photosensitivity. An aromatic group or an alicyclic aliphatic group in which the -COOR2 group and the -CONH- group are ortho to each other. The tetravalent organic group represented by X is preferably an organic group having an aromatic ring having 6 to 40 carbon atoms, and more preferably has the following formula (14):

(14) The structure shown, but is not limited to these. Further, the structure of Xl may be 1 157416.doc 201211686, or a combination of 2 or more types. The Xi having the structure represented by the above formula (14) is particularly excellent in terms of both heat resistance and photosensitivity. In the above formula (1), the divalent organic group represented by fluorene is preferably an aromatic group having 6 to 40 carbon atoms, and examples thereof include the following formula: (15): [Chem. 17]

The structure shown and the following formula (16): 157416.doc -15- 201211686 [Chem. 18]

^24 R23

• CH ch3 ch3 tree

This is one.一曱4CH2 ch3 ch3

-^CH2-^3 si—〇—Si—^CH2^3~

In the formula, R23 and R24 each independently represent a structure represented by a methyl group (-CH3), an ethyl group (-c2h5) propyl group (-C3H7) or a butyl group (-C4H9)}, but are not limited thereto. Further, the structure of Yi may be a species or a combination of two or more. It is represented by the above formulas (15) and (16) that the structure Y is particularly excellent in terms of heat resistance and photosensitivity. With respect to m2, the above formula (7) is preferably a gas atom or a methyl group. From the viewpoint of photosensitivity, WR5 is preferably a gas atom. Further, in view of the optical characteristics of 157416.doc 201211686, mi is an integer of 2 or more and 1 〇 or less, preferably 2 or more and 4 or less. In the case of using a polyimide precursor as a resin, examples of the photosensitive property of the photosensitive resin composition include an ester bond type and an ion bond type. The former is a polyimine precursor. a method in which a side chain of a substance is introduced into a photopolymerizable group, that is, a compound having an olefinic double bond, by an ester bond, the latter being an amino group of a carboxyl group of a polyimide precursor and an amine group having an amine group. A method of bonding by an ionic bond and imparting a photopolymerizable group. The above-mentioned ester-bonded polyimine precursor is obtained by the following method: First, an alcohol having a tetracarboxylic acid X! and a photopolymerizable unsaturated double bond and optionally an alcohol having a photopolymerizable unsaturated double bond Reaction of a saturated aliphatic alcohol having a carbon number of 1 to 4 to prepare a partially esterified tetradecanoic acid (hereinafter, also referred to as an acid/ester), and then reacting it with a diamine having the above divalent organic hydrazine The guanamine polycondensation is carried out. (Preparation of acid/ester) In the present invention, as a tetracarboxylic acid dianhydride containing a tetravalent organic group X oxime which is suitable for preparing an ester-bonded polyimine precursor, for example, isophthalic acid. Anhydride, diphenyl ether-3,3,,4,4,-tetracarboxylic dianhydride, dicuminone _3,3,,4,4,_tetramethyl phthalic anhydride, Lian _3,3| , 4,4,_tetracarboxylic dianhydride, diphenyl sulfone tetraphthalic acid dianhydride, diphenylmethane-3,3,4,4,4-tetracarboxylic dianhydride, 2,2_bis (3,4 - phthalic acid anhydride) propane, 2,2-bis (3,4-phthalic anhydride), 1,1,1,3,3,3-hexafluoropropane, etc., but is not limited thereto Of course, these may be used singly or in combination of two or more. 157416.doc •17· 201211686 In the present invention, photopolymerizable is not suitable as a precursor for preparing an ester-bonded polyimine. Examples of the alcohol which saturates the double bond include: 2-propenyloxyethanol, 1-propenyloxy-3-propanol, 2-propenylamineethanol, hydroxymethylvinylketone, 2-hydroxyethyl Vinyl ketone, 2-hydroxy_3_decyloxypropyl acrylate, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxyl acrylate _3_phenoxypropyl ester, 2-hydroxy-3-butoxypropyl acrylate, 2-hydroxy_3_t-butoxypropyl acrylate, 2-hydroxy-3-cyclohexyloxypropyl acrylate, 2 _Methyl propylene methoxyethanol, 1-mercapto propylene methoxy _ 3 - propanol, 2- methacrylamide ethanol, hydroxymethyl vinyl ketone, 2-hydroxyethyl vinyl ketone, methyl 2-hydroxy-3-decyloxypropyl acrylate, 2-hydroxy-3-3-butoxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, hydrazine hydroxy-3 Butoxypropyl propyl ester, methyl acrylate acid 2 _ _ 3 - 3 -butoxy propyl ester, 2-hydroxy-3-cyclohexyl propyl methacrylate, etc. Among the above alcohols, Mixing a part of a saturated aliphatic alcohol having a carbon number of 丨4, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, etc. The above tetracapric dianhydride suitable for the present invention is used. The esterification reaction of the acid anhydride is carried out by dissolving and mixing the above alcohol in the presence of a basic catalyst such as pyridine in a suitable reaction solvent at a temperature of 20 to 50 ° C for 4 to 10 hours. 'Get what you need As the above-mentioned reaction solvent, those which are completely dissolved in an acid/ester body and a polycondensed imine precursor which is a polycondensation product of a guanamine with a monoamine component are exemplified by N-A. Base 2-pyrrolidone, N,N_: mercaptoacetamide, N,N-dimethylformamide, dimercaptoarylene, tetramethylurea, butyrolactone 157416.doc •18·201211686 et al. Examples of the other reaction solvent include, for example, _ s, vinegar, internal vinegar, butterfly, and functional hydrocarbons, and examples of the hydrocarbons include a propyl group, a methyl ethyl group, a methyl isobutyl group, and a ring.嗣, acetic acid, acetyl acetate, acetic acid butyl vinegar, oxalic acid diethyl hydrazine, ethylene glycol dimethyl hydrazine, diethylene glycol dimethyl mystery, tetrahydrofuran, two gas, and sulphur Appearance, dichlorobutane, gas benzene, o-dichlorobenzene, hexane, gem, benzene, toluene, xylene, etc. These may be used singly or in combination of two or more. (Preparation of polyaniline precursor) 2 Under ice cooling, 'in the above acid / 8 body (typically the solution in the above reaction solvent), put a suitable dehydrating condensing agent, such as bicyclocarbodiimide , ethoxylated 2-ethoxy {2. dihydroindenyl, i, bis-dioxy-di-1,2,3-benzotriazole, N,N,-dibutyl醯iminocarbonate or the like is mixed and the acid/ester body is made into a polyanhydride, and then the diamine containing divalent organic hydrazine which is preferably used in the present invention is added dropwise or dissolved in The other solvent is used, and the guanamine polycondensation is carried out, thereby obtaining the target polyimine precursor. The diamine containing a divalent organic group, which is preferably used in the present invention, may, for example, be a p-diamine, m-phenylenediamine, 4,4-diaminodiphenyl ether or 3'4- Aminodiphenyl ether, 3,3,-diaminodiphenyl ether, 4,4,-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,31_ Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,4,-diaminodiphenylphosphonium, 3,3,-diaminodiphenylphosphonium, 4, 4,-Diamino-based stupid, 3,4,-diaminobiphenyl, 3,3,-monoaminobiphenyl, 4,4'-diaminodibenzophenone, 3,4,·2 Aminobiphenyl 157416.doc 201211686 ketone, 3,3·-diaminobenzophenone, 4,4,-diaminodiphenyl decane, 3,4,-diaminodiphenyl fluorene Alkane, 3,3,-diaminodiphenylnonane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1, 3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl] hard, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4_bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenyloxy)biphenyl, bis[4-(4-aminophenoxy)phenyl ϋ, bis[4-(3-aminophenoxy) phenyl], i, 4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2, 2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenyloxy)phenyl)hexafluoropropane, 1,4-double (3-Aminopropyldimethylmethylalkyl)benzene, o-anisidine, 9,9-bis(4-aminophenyl)anthracene, and one of the hydrogen atoms on the benzene ring Substituents such as ethyl, ethyl, hydroxyindenyl, hydroxyethyl, halogen, etc., such as 3,3'-dimethyl-4,4,diaminobiphenyl, 2,2'-dimethyl-4,4 '-Diaminobiphenyl, 3,3,-dimethyl-4,4,-diaminodiphenylmethane, 2,2'-dimethyl-4,4'-diaminodiphenyl Methane, 3,3,-dimethoxy-4,t-diaminobiphenyl, 3,3'-digas-4,4'-diaminobiphenyl, and mixtures thereof, but not Limited to this. Further, in order to improve the adhesion of the resin layer formed on the substrate to the substrate by applying the photosensitive resin composition of the present invention to the substrate, it is also possible to prepare a polyimide precursor. 1, 3-bis(3-aminopropyl)tetramethyl-alkaline-oxygenated, 1,3-bis(3-aminopropyl)tetraphenyl oxalate, diamine oxime Copolymerization. After the completion of the polycondensation reaction of the decylamine, if necessary, the water-absorbing by-products of the 157416.doc • 20· 201211686 dehydrating condensing agent coexisting in the reaction solution are separated by filtration, and the water, the aliphatic lower alcohol, or a mixture thereof is bad. The solvent is supplied to the obtained polymer component, and the polymer is analyzed, and then re-dissolved, reprecipitated and precipitated, etc., thereby purifying the polymer and vacuum drying, and separating the knife by the knife. Polyimine precursor. In order to increase the degree of purification, the quarantine may also be passed through a column packed with an anion and/or a cation exchange resin swelled with a suitable organic solvent to remove ionic impurities. On the other hand, the above ion-bonded polyimine precursor is typically obtained by reacting tetracarboxylic acid: gf with two materials. In this case, at least one of the core and the rule 2 in the above formula (11) is a hydroxyl group. The tetracarboxylic acid dianhydride t-diester is preferably a diamine containing a structure of the above formula (15) or (16). The photopolymerizable group is imparted by ionic bonding of a silk to an amine group by adding the following amine group-containing (meth)acrylic acid compound to the obtained polyamide precursor. ^ When the molecular structure of the above vinegar-bonded type and the above-mentioned ionic-bonded type of polyamidene precursor is measured by gel permeation chromatography and measured by a polystyrene-equivalent weight average molecular weight, it is preferably 8,000. ~150,000, better for 9'〇〇〇~50,_. When the weight average molecular weight is 8, _ or more, the physical properties are good, and when it is 150 or less, the resolution of the pattern in the developing solution is good. As a developing solvent for the gel permeation chromatography method, it is recommended that each of the tetrahydrofuran and the methylidene group be burned. Further, the weight average molecular weight was determined based on a calibration curve using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended that 157416.doc •21· 201211686 be selected from the organic solvent standard sample STANDARD SM-105 manufactured by Showa Denko. [Polyinamide] Further, an example of the preferred (A) resin in the photosensitive resin composition of the present invention has the following formula (3):

(3) where X2 is a trivalent organic group having a carbon number of 6 to 15, and Y2 is a divalent organic group having a carbon number of 6 to 35, and may be the same structure, or may have a plurality of structures, & A polyamine having a structure of a carbon number of 3 to 20 and having an organic group of at least one radical polymerizable unsaturated bond group, and n2 is an integer of from 1 to 1,000. The polyamine is preferably used as a negative photosensitive resin composition. In the above formula (3), as the group represented by I, in terms of both photosensitive property and chemical resistance, it is preferably the following formula (17), [Chemical 20] 」"-r25 ( 17) wherein R25 is a group represented by an organic group having at least one radical polymerizable unsaturated bond group having 2 to 19 carbon atoms. 157416.doc -22· 201211686 In the above 6 to 3, the trivalent organic group represented by X2, preferably a carbon number base, is preferably selected from the following formula: [Chem. 21]

The aromatic group in the group represented by Xr (18), and more preferably the aromatic group in which the carboxyl group and the amine group are removed from the structure of the filament-substituted isophthalic acid. In the above formula (7), as the divalent organic group represented by Y2, an organic group having a carbon number of 6 to 35 is preferable, and further preferably, it has four substituted groups - an aromatic ring or a fat. A cyclic organic group of a family ring, or a polymorphic or anthracene group. As a valence organic compound represented by γ :: the following general formula (15) and the following general formulas (19) and (20): [Chem. 22]

157416.doc -23· 201211686

[Chem. 23]

^27 R26

Wherein R26 and R27 are each independently a group selected from the group consisting of a hydroxyl group, a methyl group (even), an ethyl group (-C2H5), a propyl group (<3屮) or a butyl group, and Propyl and butyl contain various isomers}

[化 24J

^28 -(~CH

/Sm,+CH2k: nCH^ -tCHz

Towel 4 CH〇- 157416.doc -24- 201211686

In the formula, nu is an integer of 0 to 8, and is called an integer of 〇~3, respectively, m7 and an integer of 〇~1〇, respectively, and R28 and r29 are methyl (-CH3), B. Base (_c2H5), propyl (_c3H7), butyl (-C4H9) or such isomers}. As the aliphatic group or the decyloxy group having no cyclic structure, the following general formula (21) is preferably exemplified: [Chem. 25] +CH2V9 fCH2—CH2—%〇CH2-ch2- /mu 〒30 -Si —0· R32 R31 R33 (2 1) {wherein ni9 is an integer from 2 to 12' 〇110 is an integer from 1 to 3, called 丨 is an integer from 1 to 20' and R3〇, R31, R_32, and R_33 are respectively Independently a carbon number of 1 to 3 or a substituted phenyl}. The polyamine resin of the present invention can be synthesized, for example, by the following manner. (Synthesis of a phthalic acid compound sealing body) First, a compound having a trivalent aromatic group X2, for example, a phthalic acid substituted with an amine group, a phthalic acid substituted with an amine group, and 157416.doc -25- 201211686 At least one or more compounds of the group consisting of amino-substituted terephthalic acid (hereinafter referred to as "the "dicarboxylic acid compound" molar reacts with the compound 1 which reacts with the amine group 'A compound in which the amine group of the phthalic acid compound is modified and sealed by a radical having a radically polymerizable unsaturated bond (hereinafter referred to as "phthalic acid compound sealing body"). When the phthalic acid compound is sealed by the above-mentioned radical containing a radically polymerizable unsaturated bond, it is possible to impart negative photosensitivity (photocurability) to the polyamine resin. The group containing a radically polymerizable unsaturated bond is preferably an organic group having a radically polymerizable unsaturated bond group having 3 to 20 carbon atoms, particularly preferably a group containing a methyl propylene or a propylene group. Said The stupid one-glycol compound sealant can be obtained by using an amine group of a phthalic acid compound and a brewing gas having at least one radical polymerizable unsaturated bond group having a carbon number of 3 to 20, or isocyanic acid. Oxygen compounds and the like are obtained by reaction. As a preferred brewing chlorine, there may be mentioned: (?) propylene-brewed chlorine, 2-[(methyl)propenyloxy]ethane, 3_[(meth)acryloxyloxy ] propane gas, bismuth chloroformate methyl) propylene oxy] ethyl acetonate, chloroformic acid 3_[(methyl) propylene oxide oxy] propyl hydrazine. Preferred examples of the isocyanate vinegar include (meth)acrylic acid ethoxyacetic acid, isocyanate, rhodium methyl) propylene oxymethyl] ethyl hydrazine, isocyanate 2-[ 2-(Methyl)acryloxyethoxyethoxy]ethyl ester or the like. Preferred examples of the epoxy compound include glycidyl (meth)acrylate and the like. These may be used singly or in combination, particularly preferably methyl propylene hydride I574I6.doc 26 * 201211686 Chlorine and/or 2-(methacryloxy) acetoacetate. Further, as the phthalic acid compound sealing body, the phthalic acid compound is 5-aminoisophthalic acid, and since it is excellent in photosensitive properties and is excellent in film properties after heat curing, it is preferred. . The above-mentioned hydrazine sealing reaction can be carried out by stirring and dissolving a phthalic acid compound and a sealant in a solvent in the presence of a basic catalyst such as pyridine or a tin-based catalyst such as di-n-butyltin laurate. . As the reaction solvent, it is preferred to completely dissolve the phthalic acid compound sealing body as a product, and examples thereof include N-methyl-2-pyrrolidone, N,N-methylammoniumamine, and N,N. Methylformamide, dimethyl sulfoxide, tetramethylurea, γ-butyrolactone, and the like. Examples of the other reaction solvent include a ketone, a § | a class, an internal drug, and a chemistry. Examples of the hydrocarbons include acetone, methyl ethyl ketone, and tombs. j ater* — ^ _

Into the gasification of hydrogen. In this case,

Wait. These solvents may be used singly or in combination as needed. There is a neck ’ and the by-product in the process of sealing reaction prevents the contamination of the subsequent steps. It is preferred to temporarily re-deep the water and wash it with water or to perform appropriate purification by removing the ion-removing component by the ion column, which is filled with ion. (Synthesis of polystyrene) The above-mentioned phthalic acid compound sealant can be combined with a diamine compound having a divalent organic 157416.doc •27-201211686-based Y2 in an alkaline contact such as pyridine or triethylamine. The polyamine of the present invention is obtained by mixing in a suitable solvent in the presence of a solvent and carrying out polycondensation of the guanamine. As a method of polycondensation of a guanamine, a method of mixing a diamine compound by using a dehydrating condensing agent, making a phthalic acid compound sealing body into a symmetric polyanhydride, or sealing a phthalic acid compound by a known method is exemplified. A method of mixing a diamine compound after chlorination, a method of reacting a buplenic acid component with an active acetalizing agent in the presence of a dehydrating condensing agent, and actively esterifying the diamine compound. As the dehydrating condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxymethyl-2-ethoxy 10 dihydroindenyl, m-carbon dioxy--1 , 2,3-benzotriazole, n, n,-d-butylenedimino carbonate, and the like. Examples of the gasifying agent include sulfinium gas and the like.乍 is an active esterifying agent', which may be exemplified by N-hydroxybutadienimide or hydroxy-hydroxyl-and-situ-based-5-norborn dilute _2,3-di-sodium sulphate, 2-perylene Imino-2-cyanoacetic acid Bs, 2-transiminoimido-2-cyanoacetic acid, and the like. The diamine compound having an organic group Y2 is preferably selected from the group consisting of an aromatic fluorenyl aromatic bisamine benzophenone compound, an alicyclic diamine compound, a direct bond aliphatic diamine compound, and a sulphuric acid. The diamine compound in the group consisting of the diamine compounds may be used in combination as needed. Examples of the aromatic diamine compound include p-phenylenediamine, isophthalic acid. 4'4 monoaminodiphenyl ether 3,4,-diaminodiphenyl ether, diamine phenyl ether, 4, 4 '-Diaminodiphenyl sulfide, 3,4,•Diaminodiphenylsulfide 157416.doc •28· 201211686 Ether, 3,3'-diaminodiphenyl sulfide, 4,4· -diaminodiphenyl sulfone, 3,4·-diaminodiphenyl sulfone, 3,3·-diaminodiphenyl fluorene, 4,4′·diaminobiphenyl, 3,4· -diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodibenzophenone, 3,4'-diaminodibudecone, 3,3·- Aminobis ketone, 4,4'-diaminodiphenyl decane, 3,4·-diaminodiphenyl decane, 3,3'-diaminodiphenyl decane, 1 , 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4 -(4-Aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4'-bis(4-aminophenoxy)biphenyl , 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy) Phenyl]ether, 1,4-double (4 -aminophenyl) stupid, l,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl) Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4- (4-Aminophenoxy)phenyl]hexafluoropropane, iota, 4-bis(3-aminopropyldimethylmethylalkyl)benzene, o-benzidine sulfone, 9,9-bis (4 _aminophenyl) hydrazine, and one of the hydrogen atoms on the benzene ring is one or more selected from the group consisting of a methyl group, an ethyl group, a hydroxymethyl group, a hydroxyethyl group, and a methoxyl group. a substituted diamine compound. Examples of the diamine compound substituted with a hydrogen atom on the benzene ring include 3,3'-dimethyl-4,4'-diaminobiphenyl and 2,2'-dimethyl-4. , 4,-diamino phenyl, 3,3'-dimercapto-4,4,-diaminodiphenyl decane, 2,2'-diindolyl-4,4'-diamino Diphenyldecane, 3,31-dimethoxy-4,4,-diaminobiphenyl, 3,3'-di-gas-4,4,-diaminobiphenyl, and the like. As the aromatic bisaminophenol compound, there may be mentioned: 3,3,-dihydroxyl linkage 157416.doc •29-201211686 aniline, 3,3,diamino-4,4i-dihydroxybiphenyl, 3,3 ,_Dihydroxy-4,4,-diaminodiphenyl sulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl) ) propane, 2,2_bis-(3-amino-4-ylhydroxyphenyl)hexafluoropropane, 2,2-bis-(3-hydroxy-4-aminophenyl)hexafluoropropane, double _( 3-hydroxy-4-aminophenyl)methane, 2,2-bis-(3-hydroxy-4-aminophenyl)propane, 3,3'-di-diyl-4,4'-diamino Benzophenone, 3,3,-dihydroxy-4,4,_:aminodiphenyl ether, 4,4'-dihydroxy-3,3,-diaminodiphenyl ether, 2,5-di Hydroxy-1,4-diaminobenzene, 4,6-diaminoresorcinol, iota, bis-(3-amino-4-hydroxyphenyl)cyclohexane, 4,4-(α -Methylbenzylidene)-bis(2-aminophenol) or the like. Examples of the alicyclic diamine compound include 1,3-diaminocyclopentane, 1,3-diaminocyclohexane, and 1,3-diamino-1-indenylcyclohexane; , 5-diamino-1,1-dimethylcyclohexane, 1,5-diamino-indole, 3-dimethylcyclohexane, 1,3-diamino-1-indenyl- 4-isopropylcyclohexane, 1,2-diamino-4-methylcyclohexane, 1,4-diaminocyclohexane, 1,4-diamino-2,5·diethyl Cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomercapto)cyclohexane, 2-(3-aminocyclopentyl)-2-propylamine , menthane diamine, isophorone diamine, norbornane diamine, 1-cycloheptene-3,7-diamine, 4,4·-methylene bis(cyclohexylamine), 4,4 ·-methylene bis(2-methylcyclohexylamine), 1,4-bis(3-aminopropyl) piperene, 3,9-bis(3-aminopropyl)-2,4, 8,10-tetraoxa-[5,5]-undecane, and the like. The linear aliphatic diamine compound may, for example, be 1,2-diaminoethane, 1,4-diaminobutane, 1,6-diaminohexane or 1,8-diaminooctyl a hydrocarbon type diamine such as an alkane, 1,1 - diamino decane or 1,12-diaminododecane, or 2-(2-aminoethoxy)ethylamine, 2,2'-( An oxyalkylene type diamine such as ethyldioxy)diethylamine or bis[2-(2-aminoethoxy)ethyl]ether is exemplified. 157416.doc -30· 201211686—As a oxo-alkane diamine compound, dimethyl (poly) decane hydride is exemplified by 商标 ° Yue Chemical Industrial Co., Ltd. under the trade names PAM-E, KF-8010, X-22 -161A, etc. As the reaction solvent, a solvent which completely dissolves the produced polymer is preferably exemplified by N-methyl-2-pyrrolidone and N,N-dimethylacetamide n'n-mercaptodecylamine. Dimercaptopurine, tetradecylurea, butane vinegar, etc. Further, ketones, esters, lactones, ethers, hydrocarbons, and hydrocarbons may be used as a reaction solvent depending on the case. Specific examples thereof include acetone, methyl ethyl ketone 'mercaptoisobutyl ketone, cyclohexanone, decyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, ethylene glycol dimethyl ether, and Ethylene glycol dioxime ether, tetrahydrofuran, dioxane, hydrazine, 2_dioxaethane, hydrazine _ dibutane, chlorobenzene, o-dichlorobenzene, hexane, heptane, benzene, benzene, bis Benzene and so on. After completion of the polycondensation reaction of the guanamine, the precipitate derived from the dehydration condensing agent or the like may be separated by filtration if necessary. Then, a poor solvent of polyamine such as water or an aliphatic lower alcohol or a mixed solution thereof is added to the reaction liquid to precipitate polyamine. Further, the polyphosphate which is precipitated is re-dissolved in a solvent and reprecipitated and precipitated. The purification is carried out and vacuum drying is carried out to separate the target polyamine. Further, in order to further improve the degree of purification, the solution of the polyamine may be passed through a column packed with an ion exchange resin to remove ionic impurities. The polystyrene-equivalent weight average molecular weight of the gelatinization chromatography (hereinafter referred to as "GPC") of polyamine is preferably 7,000 to 70,000, and further 157,416.doc •31·201211686 is preferably 1 〇, 〇〇 〇~50,00 (^) The basic physical properties of the hardened convex pattern are ensured as long as the weight average molecular weight is 7,000 or more in terms of polystyrene. Developing solubility. As a solution of GPC, tetrahydrofuran or N_mercapto-2-pyrrolidinone is recommended. Further, the weight average molecular weight value is determined according to a calibration curve prepared using standard monodisperse polystyrene. The polystyrene is preferably selected from the standard sample SM-105 of an organic solvent manufactured by Showa Denko. [Polyp-azole precursor] Further example of the preferred (A) resin in the photosensitive resin composition of the present invention To have the following general formula (4): [Chemical 26] ΟΗ A BU-CO-X3-C〇NH-Y3 is called CO-X4-COMH-Y4-NH-OH^--n3__ where Y3 is 4-valent organic with carbon atoms Preferably, the tetravalent organic group ''4', χ3 and χ4 having two or more carbon atoms are each independently a divalent organic group having two or more carbon atoms' η3 is an integer of 1 to 1 ,, ... is ❽ An integer of ～500, η3/(η3+ η4)>0.5, and a structure including χ3 and γ32η3 dihydroxydiamine units and n4 diamine units containing X4 and Y4 are not limited. The poly-β-azole precursor (hereinafter, the polycarbazole precursor represented by the above formula (4) is simply referred to as "poly-p-azole precursor" 157416.doc -32* 201211686). The polymer precursor may be a polymer having the above-mentioned base bis-amine in the general formula (4) and a case where only the di-mercaptoamine unit is present on the right, and may have the above formula (4, Φ 夕 Jm) ) II 4 diamine units of T (hereinafter, there is a case where only a diamine unit is used). In order to obtain the photosensitive property, the number of carbon atoms of Χ3 is preferably two or more and four or less, and in order to obtain the photosensitive property, the number of carbon atoms of & is preferably two or more and 40 or less 'for obtaining the photosensitive property' γ3 carbon The number of atoms is preferably two or more and less than one and that in order to obtain photosensitive characteristics, the number of carbon atoms of L is preferably two or more and 40 or less. The monohydroxyl-amine unit can be obtained by using a diaminodihydroxy compound having a structure of γ3(ΝΗ2) 2 (〇Η, preferably a bisaminophenol) and a structure having X3(COOH) 2 The synthesis of a carboxylic acid is carried out. Hereinafter, a typical aspect will be described by taking the above-mentioned diaminodihydroxy compound as a bisaminophenol as an example. The two groups of the amino group of the bisaminophenol and the hydroxyl group are adjacent to each other'. The dihydroxydiamine unit is ring-closed by heating under the armpit, and is changed into a heat-resistant polyoxazole structure. In order to obtain the photosensitive property, the sum in the formula (3) is 1 or more. In order to obtain the photosensitive property, the following β n3 is preferably in the range of 2 to 1000, more preferably in the range of 3 to 50, and most preferably in the range of 3 to 20. The poly, azole precursor is also needed as needed. N4 of the above-mentioned diamine units may be condensed. The diamine unit may be formed by synthesis of a diamine having a structure of y4(nh2)2 and a dicarboxylic acid having a structure of X4(COOH)2. (3) 114 is a range of 〇~5〇〇, and good sensitization characteristics are obtained by n4 being 500 or less. n4 is more preferably 〇~1 The range of 0. If the ratio of the arylamine unit to the diamino group 157416.doc •33·201211686 is too high, the solubility in the alkaline aqueous solution used as the developer is decreased, so the formula 3) The value of ～/(~ + η#) is more than 〇5, more preferably 0.7 or more, and most preferably 0.8 or more. As a diamine group having a structure of Υ3(ΝΗ2)2(〇Η)2 Examples of the bisaminophenol of the hydroxy compound include 3,3 dihydroxybenzidine, 3,3,-diamino-4,4'-dihydroxybiphenyl, and 4,4'-diamino-3. 3,-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4,-diamino-3 3,3,-dihydroxydiphenyl, Bis-(3-amino-4-transphenyl) oxime, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino- 4-hydroxyphenyl)hexafluoropropane, 2,2-bis-(4-amino-3-phenylphenyl)hexafluoropropane, bis-(4-amino-3-ylhydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4,-diamino-3,3,-dihydroxybenzophenone, 3,3,-diamino group_ 4,4, dihydroxy dicotone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether 3,3,-diamino-4,4,-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxy stupid, ι,3-diamino _ 2,4-di A benzene, a 1,3-diamino-4,6-di-diylbenzene, etc. These bisaminobenzenes can be used individually or in combination of 2 or more types. In terms of the photosensitive property, the 3-base is preferably the following formula (22): [Chem. 27]

157416.doc •34- 201211686 The one shown. Further, examples of the diamine having a structure of Υ4(ΝΗ2)2 include an aromatic diamine and decanediamine. Examples of the aromatic diamine include, for example, a stupid monoamine, a p-diamine, a 2,4-methyldiamine, a 3,3'-diaminodiphenyl hydrazine, and a 3,4'-diamino group. Diphenyl ether, 4,4'-diaminodiphenyl ether, 3,3i-diaminodiphenyl sulfonium, 4,4,-diaminodiphenyl sulfone, 3,4,-diaminodi Stupid base, 3,3,_monoamine-phenyl- ketone, 4,4·-diaminodiphenylmethane, diamine-based ketone, 4,4'-diamine Phenyl sulfide, 3,3'-diaminodiphenyl ketone, 4'4·-diaminodiphenyl ketone, 3,4·-diaminodiphenyl ketone, 2,2,-double (4-Aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 153_bis(3-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy)benzene, i,4_bis(4-aminophenoxy)benzene, 4-mercapto-2,4-bis(4-aminophenyl)-1-pentene, 4_ Mercapto-2,4-bis(4-aminophenyl)-2-pentyl, 1,4-bis(α,α-didecyl-4-aminobenzyl)benzene, imino group- Di-p-phenylenediamine, 15-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2,4-bis(4-aminophenyl)pentane, 5 (or 6)- Amino-1-(4-aminophenyl)-1,3,3- Triterpene indane, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazo, 4,4,-diaminodiphenylurea, 4,4,-bis (4 -aminophenoxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)benzene Hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]benzophenone, 4,4,-bis(4-aminophenoxy)diphenyl sulfone , 4,4'-bis[4-(α,α-dimercapto-4-aminobenzyl)phenoxy]benzophenone, 4,4·-bis[4-(α,α-二Mercapto-4-aminobenzyl)phenoxy]diphenylsulfone, 4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, phenylindanediamine, 3,3·_Dimethoxy· 157416.doc •35· 201211686 4,4·-Diaminobiphenyl, 3,3,_Dimethyl-4,4,-diaminobiphenyl, ortho Aniline sulfone, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl)sulfone, bis(4-aminophenoxyphenyl) sulfide, όAminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl)benzene, 99-bis(4-aminophenyl), 4,4·-di-(3 -aminophenoxy)diphenylanthracene, 4,4,_di a benzoyl aniline or the like, and a hydrogen atom of an aromatic nucleus of the aromatic diamine is selected from the group consisting of a gas atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group, a cyano group, and a phenyl group. At least one base or atom substituted compound. Further, as the above-mentioned one amine, in order to improve the adhesion between the two and the substrate, it is possible to select a diarrhea diamine. Examples of the stilbene diamine include bis(4-aminophenyl)dimethyl decane, bis(4-aminophenyl)tetramethyl decane, and bis(4-aminophenyl) four.基 dioxane, bis(γ-aminopropyl)tetramethyldioxane, 1>4•diaminopropyldimethylmethylalkyl)benzene, bis(4-aminobutyl) Tetrakisyl dioxime*, bis(γ-aminopropyl)tetraphenyldioxane, and the like. Further, as a preferred dicarboxylic acid having a structure of X3(COOH)2 or X4(COOH)2, an aliphatic group or an aromatic group having a linear, branched or cyclic structure of X3 and X4, respectively, may be mentioned. In particular, it is preferred to contain an organic ring having two or more carbon atoms of an aromatic ring or an aliphatic ring, and each of χ and X / is preferably selected from the following formula (23): 4 ] 157416.doc •36- 201211686

In the formula, the R34 table is not selected from the divalent group in the group consisting of _CH2_, -〇-, -S-, -S〇2_, -CO-, -NHCO-, and -C(CF3)2- The aromatic group shown is preferred in terms of photosensitivity. The polycarbazole precursor can be a terminal organic group that is sealed with a particular organic base. In the case of using a poly-p-azole precursor sealed by a sealant, it is expected that the mechanical properties (especially elongation) and the shape of the cured projection pattern of the coating film after heat curing of the photosensitive resin composition of the present invention become good. As a preferred example of such a sealing group, the following formula (24) can be cited:

157416.doc -37- 201211686 The one shown. The polystyrene conversion weight average molecular weight is preferably 3, _~7G, _, more preferably 6 〇〇〇 5 5 00. From the viewpoint of the physical properties of the hardened convex pattern, the weight average molecular weight is preferably 3 or more. χ, in terms of resolution, it is preferably 70, and coffee is used as a developing solvent for gel permeation chromatography. South, N-methyl · 2♦ each burning _. Further, the molecular weight was determined by calibration (4) of standard 単 dispersed polystyrene production. As standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, a standard sample of organic solvents manufactured by Showa Denko. [Polyimine] Further, an example of the preferred (A) resin in the photosensitive resin composition of the present invention has the above formula (5):

Kl· 2ΟΛχβοΑγοί Ν V5- m3 άβ) n5 (wherein, X5 represents a 4 to 14-valent organic group 'Ys represents a 2 to 12-valent organic group, and r7 represents at least one selected from a divalent hydroxyl group, a sulfonic acid group or a thiol group. The organic group based on the group, and may be the same or different ' ns is an integer of 3 to 200 00, and ^ and is an integer represented by 〇 ~ 1 )). Here, the resin of the formula (5) exhibits sufficient film properties and does not require chemical changes in the step of heat treatment, and is therefore suitable for processing at a lower temperature. 157416.doc -38 - 201211686 good. In the structure of the above formula (5), the X5 in the structure of the monovalent to 14-valent organic group is preferably 4 to 40 in the carbon number 4 _ soil', and has both heat and sensitivity, and Η: 夕古γ? ?·— Further preferably with right--, 忒元特〗 〖Life and Lu, machine some. The polytetramethylene imine represented by the above formula (5) having a carbon number of 5 to 40 in the aromatic ring or the aliphatic ring can be obtained by making tetracarboxylic acid, corresponding to a human: -, tetracarboxylic acid Diacetate or the like is obtained by reacting a diamine and a corresponding diisocyanate 'dimethyl ketone diamine. Polyphthalocyanine is obtained by the use of polyamines, which are usually used as a polyimine precursor, which is reacted with diamines and diamines, by heating or using chemicals such as acids or bases. The treatment is carried out for dehydration closed loop Preferred examples of the tetradecanoic acid dianhydride include pyromellitic dianhydride, 3,3,4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3,4,_biphenyltetra Formic acid dianhydride, 2,2',3,3·-biphenyltetracarboxylic dianhydride, 3,3,,4,4·-benzophenone tetracarboxylic dianhydride, 2,2,,3,3, -diphenyl fluorenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propanone-if, 2,2-bis(2,3-monophenyl) propylene dianhydride 1,1 _bis(3,4-dibuylphenyl)ethane dianhydride, 1,1-bis(2,3-di-rebase) dianhydride, bis (3,4-di) Carboxyphenyl)decane dianhydride, bis(2,3-dicarboxyphenyl) phthalic anhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, bis(3,4·dibuxobenzene) Base) di-hepatic, 1,2,5,6-carotene-hepatic, 9,9-bis(3,4-dipyridylphenyl) phthalic acid dianhydride, 9,9-double {4- (3,4·dicarboxyphenoxy)phenyl}acid dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-«pyridinic acid dianhydride, 3,4,9,10_茈tetradecanoic acid dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, etc. Aromatic tetramethyl 157416.doc 39· 201211686 Acid dianhydride Or butane tetra Aliphatic tetracarboxylic acid dianhydride such as acid dianhydride, 1,2,3,4-cyclopentane tetracarboxylic acid di-hepatic acid, 3,3,,4,4'-diphenyl sulfone tetradecanoic acid and the following Equation (25): [Chem. 31]

Wherein R35 represents a group selected from an oxygen atom, c(cf3)2, c(ch3)2 or lycopene 2, and R36 and R37 may be the same or different and represent a hydrogen atom, a hydroxyl group or a thiol group. The compound shown by the base}. Among these, 3,3,4,4·-biphenyltetraphthalic acid dianhydride, 2,3,3,4,4-biphenyltetracarboxylic dianhydride, 2, 2, 3, 3,-biphenyltetracarboxylic dianhydride, 3,3',4,4,-benzophenonetetracarboxylic dianhydride, 2,2,3,3'-dibenzophenone tetracarboxylic dianhydride, 2, 2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl) Ethane dianhydride, 1, bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl) Methane dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Hexafluoropropane dianhydride, 3,3,,4,4,-diphenylphosphonium tetraphthalic acid dianhydride, 9,9-bis (3,4-157416.doc -40· 201211686 dicarboxyphenyl) acid Dihydride, 9,9-bis{4-(3,4·dicarboxyphenoxy)phenyl}phthalic acid dianhydride and the following formula (26) [Chem. 32] R40

(2 6) wherein R38 represents a group selected from an oxygen atom, C(CF3)2, C(Ch3)2 or S02, and R39 and Rw may be the same or different and represent a hydrogen atom, a hydroxyl group or An acid dianhydride of the structure shown by the group of a thiol group. These may be used singly or in combination of two or more. Ys of the above formula (5) represents a structural component of a diamine, and the diamine represents a 2- to 12-valent organic group containing an aromatic ring or an aliphatic ring, and among them, an organic group having 5 to 40 carbon atoms is preferred. . Specific examples of the diamine include 3,4,-diaminodiphenyl ether, 4,4,-diaminodiphenyl ether, and 3,4,-diaminodiphenyl decane, 4. 4,-Diaminodiphenylnonane, 3,4'-diaminodiphenylsulfone, 4,4ι-diaminodiphenylphosphonium, 3,4'-diaminodiphenyl sulfide , 4,4,-diaminodiphenyl sulfide, hydrazine, bis(4-aminophenoxy)benzene, benzyne, m-phenylenediamine, p-phenylenediamine, anthracene, 5-naphthalenediamine, 2,6·naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, double {4-(4-Aminophenoxy)phenyl}ether, 14-bis(4-aminophenoxy)benzene, 2,2ι-dimethyl-4,4-monoaminobiphenyl, 2 , 2'-diethyl_4,4,diaminobiphenyl, 3,3'-diguanide 157416.doc •41- 201211686 keto-4,4'-diaminobiphenyl, 3,3, -diethyl-4,4,-diaminobiphenyl, 2,2,,3,3,-tetradecyl_4 4,-- & '-aminobiphenyl, 3,3',4 , 4, tetramethyl-4,4,-diaminobiphenyl, 2,2丨-bis(trisulphonyl)-4,4'-diaminobiphenyl, 9,9-bis (4- Aminophenyl) oxime or such aromatic Ring substituted by the group or hospital compound ώ element atoms or aliphatic diamine _ $ hexyl group, an alkylene group dicyclohexylamine Yue following general formula (27): [Formula 33]

Wherein R41 represents a group selected from an oxygen atom, C(CF3)2, C(CH3)2 or S02 and R42 to R45 may be the same or different 'and represents a hydrogen atom, a hydroxyl group or a thiol group. A diamine or the like of the structure shown by the base}. 157416.doc • 42- 201211686 Among these, preferably 3,4,diaminodiisopropyl ether, 4,4,diaminodiisopropyl ether, 3,4'-diaminodiphenyl A hospital, 4,4, diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfonium, 4,4,-diaminodiphenyl sulfone, 3,4,-diamine Yidiphenyl sulfide, 4,4'-diaminodiphenyl sulfide 'm-phenylenediamine, p-diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 9,9 _Bis(4-aminophenyl) and the following formula (28): [Chem. 34]

Wherein r46 represents a group selected from an oxygen atom, c(cf3)2, c(ch3)2 or so2, and R47~Rsq may be the same or different and represent a group selected from a hydrogen atom, a hydroxyl group or a thiol group. A diamine of the structure shown by the group}. Among the shai, etc., particularly preferred are 3,4'-diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl, 3,4, diaminodiphenyl ether, 4,4,-two Aminodiphenylnonane, 3,4·diaminodiphenylphosphonium, 4,4′-diaminodiphenylsulfone, anthracene, 4-bis(4-aminophenoxy 157416.doc • 43· 201211686 base) benzene, and the following general formula (29): [Chem. 35]

(2 9) a diamine of the structure of C(CH3)2 or S〇2 and R5 2 and Rs 3 which are the same or different and which represent a structure selected from a hydrogen atom, a trans group or a thiol group} . These may be used singly or in combination of two or more. R7 and Rs of the formula (5) represent a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. In the present invention, 'as R? and Rs', a phenolic hydroxyl group, a sulfonic acid group and/or a thiol group can be mixed together. By controlling the amount of the alkali-soluble group of R7 and Rs, the dissolution rate in the alkaline aqueous solution is changed, so that a photosensitive resin composition having an appropriate dissolution rate by the adjustment can be obtained. Further, in order to improve the adhesion to the substrate, the aliphatic group having the oxime structure of X5 and Y5 can be copolymerized in a range in which the heat resistance is not lowered. Specifically, examples of the diamine component include bis(3-aminopropyl)tetramethyldioxane and bis(p-aminophenyl)octamethyl-5 copolymerized with 丨~(7) mol%. Such as oxane or the like. The above-mentioned polyimine can be synthesized, for example, by reacting a tetracarboxylic dianhydride with a diamine compound (-partially substituted as a terminal of a monoamine 157416.doc • 44-201211686 sealant) at a low temperature, A method of reacting a tetracarboxylic dianhydride (the moiety is substituted with an acid anhydride or a monofluorene compound or a terminal sealant of a mono-active vine compound) with a diamine compound at a low temperature, and obtaining a tetrasyl dianhydride and a yeast And then a method of reacting with a diamine (partially substituted as a terminal sealant as a monoamine) and a condensing agent, obtaining a second purpose by using tetracarboxylic acid difuran and an alcohol, and then remaining the second (4) brewing gasification, and a method of reacting a diamine (-partially substituted as a terminal (four) agent of a monoamine) to obtain a polyimine precursor; reuse is completed by using a known brewing imidization reaction method. a method of imidization, or a method of stopping the imidization reaction in the middle, introducing a part of the quinone imine structure, and introducing one by blending the fully ruthenium imidized polymer with the polyimine precursor Part of the method of quinone imine structure. The polyimine is preferably a ruthenium iodide ratio of 15 with respect to the entire polymer constituting the photosensitive resin composition. /. In the above manner, it has a polyimine. More preferably, it is 20% or more. The term "imidization ratio" as used herein means the ratio of the ruthenium imidization of the entire polymer constituting the photosensitive resin composition. If the imidization ratio is less than 15%, the shrinkage amount during thermal hardening increases, which is not suitable for thick film production. The brewing imidization ratio can be easily calculated by the following method. First, the infrared absorption spectrum of the polymer was measured to confirm the presence of an absorption peak derived from the quinone imine structure of polyimine (near 1780 cm.1 and around 1377 cm·1). Then, the polymer was subjected to heat treatment at 350 ° C for 1 hour, and the infrared absorption spectrum after heat treatment was measured. The peak intensity near 1377 cnT1 was compared with the strength before heat treatment, thereby calculating the yttrium in the polymer before heat treatment. Amine 157416.doc -45- 201211686 conversion rate. When the molecular weight of the above-mentioned polyienimine is measured by a gel permeation chromatography in terms of polystyrene-equivalent weight average molecular weight, it is preferably 3, 〇〇〇 200 200,000, more preferably 5,000 50,000. When the weight average molecular weight is 3 Å or more, the mechanical properties are good, and when it is 50,000 or less, the dispersibility in the developer is good, and the resolution of the convex pattern is good. As a developing solvent for gel permeation chromatography, tetrahydrofuran and Ν_methyl-2-pyrrolidone are recommended. Further, the molecular weight was determined based on a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, it is recommended to select STANDARD SM-105, an organic solvent standard sample manufactured by Showa Denko. (B) Anthracene derivative The (B) anthracene derivative used in the present invention will be described. (B) Derivatives A compound in which a purine ring is a basic skeleton, and a compound derived from the skeleton is referred to as an anthracene derivative. By using (B) an anthracene derivative, the discoloration suppressing effect on copper or a copper alloy is excellent. The chemical mechanism which is excellent in discoloration inhibition effect on copper or copper alloy is not certain. It is presumed that a resin containing a nitrogen atom in a molecule and a resin containing a hetero atom such as an oxygen atom or a nitrogen atom can appropriately interact with each other by using a hydrogen bond or the like. It inhibits the excessive interaction of the resin with copper and prevents discoloration on the steel. - Specific examples of the (Β) 呤 derivative include 嘌呤, adenine, wuwu 7, hypoxanthine, scutellaria, cocoa, caffeine, uric acid, and 2,6-diamino嗓吟, 9_methyl adenine β, 2 via gland 2 7 methyl adenine, 1-mercapto adenine, N-methyl adenine, 157416.doc •46· 201211686 N,N- Dimethyladenine +, 2_fluoroadenine, 9♦ hydroxyethyl) glandular scorpion, black scorpion, N-(2-hydroxyethyl) gland.吟, 8-amino-based adenine; '6-amino-8-phenyl_9H_嘌呤, bethyl adenine, 6•ethylamino guanidine, 1-phenyl adenine, N-decyl oxime嗓呤, 7_(2_-ylethyl) uranium, N-(3-phenylphenyl) black mites, 3_ethylphenyl), black scorpion, 2 gas adenine, 5-aza Adenine, 8_azadenine, 8_azaguanine, & azaindole, 8-aza-xanthine, 8-aza-xanthine, and the like. Further, the (B) anthracene derivative is selected from the following formula (6): [Chem. 36]

In the formula, R9 is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or an alkyl group or an aromatic group having 1 to 10 carbon atoms, and r1q is a hydrogen atom, a halogen atom, and an alkoxy group having a carbon number of 1 to 6 a compound represented by a hydroxyalkyl group or an amine group substituted with an alkyl group or an aromatic group having a carbon number of (~(7), and the following formula (7): [Chem. 37]

(7) wherein Rii is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or an alkyl group or an aromatic group having 1 to 10 carbon atoms, and Ru and R13 are each independently a hydrogen source 157416.doc -47·201211686 a compound represented by a mercapto group, a mercapto group or a carbon group of 1 to 10 or an aromatic group, and the following formula (8): [Chem. 38]

Rl4

Wherein ' Ri 4 is a hydrogen atom, a halogen atom, a trans group, an amine group or an alkyl group or an aromatic group having a carbon number of 1 to 10' and R1S is a hydrogen atom, a dentate atom, and an alkoxy group having a carbon number of 1 to 6 a compound represented by a group, a hydroxyl group, a hydroxyalkyl group or an amine group substituted with an alkyl group or an aromatic group having a carbon number of 丨~1〇, and the following formula [Chem. 39]

In the formula, Rl6 is a hydrogen atom 'tooth·|halogen atom, hydroxyl group, amine group or carbon number

From the viewpoint of discoloration on the copper alloy, it is preferred.

157416.doc -48· 201211686 2-fluoroadenosine, N-(2-transethylethyl)adenine, scutellaria, n-(2-ylethylethyl)adenine, N-B Adenine, N-methyl samarium, N-(3-ethylphenyl) samarium, 8-azadenine, 8-azaguanine, 8-azaindole, and the like. Wherein, it is selected from the following formula (10): [Chem. 40] nh2 R丨广N々*N (1 〇) { wherein Rm is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or a carbon number of 1 to 10 a compound represented by an alkyl group or an aromatic group, the following formula (11): [Chem. 41]

In the formula, R2Q is a compound represented by a hydrogen atom, a hydroxyalkyl group or an alkyl group having 1 to 10 carbon atoms, and the following formula (12):

In the formula, the compound represented by a hydrogen atom, a halogen atom, a trans group, an amine group or an alkyl group or an aromatic group having 1 to 10 carbon atoms, and the following formula: 157416.doc -49-201211686 ( 13): [Chem. 43]

In the formula, R22 is a hydrogen atom, a hydroxyalkyl group or an alkyl group having a carbon number of (~(7)}. It is further preferred that at least the quinone derivative in the group consisting of the substances suppresses discoloration on the copper or copper alloy. Specific examples of the compound represented by the above formula (1G) to (13) include: no. 7, glandular sputum, scutellaria, 2,6-diamino hydrazine, 2 hydroxy gem %, 2- Methyl adenine, 2_fluoroadenine. Order, 8 · azadenine, nitrogen, uranium, 8-aza sputum, etc. Further, the hydrazine derivative is at least one compound selected from the group consisting of the compound represented by the above formula (12) and the compound represented by the above formula (13), and is adhered to copper or a copper alloy. In terms of sex, it is particularly good, and from the viewpoint of the step-by-step adhesion, t is preferably the amount of the 8_gas heterogeneous 0 or 8_azepine (B) anthracene derivative relative to the resin ι mass. 〇1〇ίί parts by mass, preferably 4G Q5~2f parts, when the above-mentioned compounding amount is 0_01 mass damage or more, exhibits discoloration on copper or copper alloy, and on the other hand 'under 10 parts by mass or less In the case of the case, the storage stability is excellent. (C) Sensitizer ' (c) The sensitizer used in the present invention will be described. (6) Photosensitive agent and the photosensitive resin composition of the invention of 157416.doc _50 201211686, for example, mainly using (iv) an imine precursor and/or polyamine as a negative type of resin, or, for example, mainly using a polycarbazole oxime and / or soluble polyimine is different as the positive type of (A) resin and the like. (C) The amount of the photosensitive resin composition to be sensitized is a part by mass with respect to (a) the photosensitive sapphire 1 enamel portion. The amount of the above-mentioned formulation is '1 part by weight or more from the viewpoint of photosensitivity or patterning, and is 50 mass from the viewpoint of the curability of the photosensitive resin 汲σ substance or the physical properties of the photosensitive resin layer after curing. The following. First, the case of the required negative type will be explained. As the (c) sensitizer in this case, a photopolymerization initiator and/or a photoacid generator are used, and as a photopolymerization initiator, a photoradical polymerization initiator is preferred, and diphenyl can be preferably used. a benzophenone, a benzoic acid, a 4-benzoic acid, a 4-benzoic acid, a 4, a benzoic acid, a benzoic acid, a benzophenone, a benzophenone, a dibenzoyl derivative, 2, 2, Acetophenone derivatives such as ethoxyacetophenone 2-carboxy-2-methylpropiophenone, hydrazine-hydroxycyclohexyl phenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthiazide Toxyl ketone, ethyl thioxanthene and other thioxanthone derivatives, benzyl derivatives such as benzyl, benzyl ketal, benzyl-β-methoxyethyl acetal, female heart, benzoin A benzoin derivative, phenyl group, butyl diketone = (o-methoxy ke group m, phenyl phenyl group - propyl bismuth - ^ o-methoxy meth), 1-phenyl 1>2. Propylenedione_2_(o-ethoxyl group), phenyl-1,2·propanedione-2_(o-phenylene), monthly loss, M-diphenylpropene Diketone-2-(o-ethoxycarbonyl)anthracene (o-benzylidene) hydrazine, etc., 1-phenyl-3-ethoxypropanetrione_2 _ N-stupylglycine and other aryl glycine 157416.doc •51· 201211686 Classes of 'peroxybenzoic acid and other peroxides such as chlorine, aromatic azoles, ferrocenes Photoacid generators such as decyloxyimido)·4-methoxy nodal cyanide, etc., but are not limited thereto. Among the above photopolymerization initiators, in particular, in terms of photosensitivity, it is more preferably an anthracene. When a photoacid generator is used as the (c) sensitizer in the negative photosensitive resin composition, it has an effect of exhibiting acidity by irradiation with active light such as ultraviolet rays, and depending on its action, the following is The crosslinking agent of the component d) is crosslinked with the resin as the component (A), or the crosslinking agent is polymerized with each other. · As an example of the photoacid generator, a diarylsulfonium salt, a triarylsulfonium salt, and a second are used. Alkyl phenyl hydrazine methyl sulfonium salt, diaryl sulfonium salt, aryl diazonium rust salt, aromatic tetracarboxylic acid ester, aromatic sulfonate, nitrobenzyl ester, sulfonic acid SB, aromatic N- An oxonium imide acid salt, an aromatic terminide, a halogenated alkyl group-containing compound, and an alkyl group-containing heterocyclic compound 'naphthoquinonediazide-4-sulfonate. Such a compound may be used in combination of two or more kinds or in combination with other sensitizers as needed. Among the above photoacid generators, in particular, in terms of photosensitivity, an aromatic sulfonium sulfonate or an aromatic glacial oxime sulfonate is more preferable. The amount of the sensitizer to be added is preferably from 2 to 15 parts by mass in terms of photosensitivity characteristics with respect to (A) 1 part by mass of the resin. When the photosensitive agent (C) is blended in an amount of 1 part by mass or more with respect to 1 part by mass of the (A) resin, the photosensitivity is excellent, and by blending 50 parts by mass or less, the thick film is excellent in hardenability. Further, as described above, when the (A) resin represented by the formula (11) is an ionic bond type, photopolymerization of a side chain of the resin is imparted to the side chain of the resin via an ionic bond, 157416.doc -52·201211686, A (meth)acrylic compound having an amine group is used. In this case, an (mercapto)acrylic compound having an amine group is used as the (c) sensitizer, and for example, preferably decylaminoethyl acrylate, dimethylaminoethyl methacrylate, and diethyl acrylate are used. Aminoethyl ester, diethylaminoethyl methacrylate, didecylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl acrylate, methyl Diethylaminopropyl acrylate, dimethylaminobutyl acrylate, dimethyl dimethyl methacrylate, diethyl butyl acrylate, diethyl butyl methacrylate And a dialkylaminoalkyl acrylate or methacrylate, wherein, in terms of photosensitivity, it is preferred that the alkyl group on the amine group is a carbon number hi0 and the alkyl chain is a carbon number of from 1 to 10 carbon atoms. Or a dialkylaminoalkyl methacrylate. The amount of the (meth)acrylic acid compound having an amine group is from 1 to 20 parts by mass based on 100 parts by mass of the (A) resin, and is preferably from 2 to 15 parts by mass in terms of photosensitivity characteristics. As (c) sensitizer, it is based on (A) resin with an (amino) acrylate compound having an amine group! When the mass is prepared in an amount of at least 1 part by mass, the photosensitivity is excellent, and the hardening property of the thick film is excellent by blending 2 parts by mass or less. The situation of the required positive type will then be explained. As the sensitizer in this case, a photo-acid generator is used, and specifically, a heavy gas-pulsing compound, a rust salt, a dentate-containing compound, or the like can be used. From the viewpoint of solvent solubility and storage stability, it is preferred to have A compound of the diazonium structure. The above diazonium compound is a compound having a 1>2_benzoquinonediazide structure or a quinone, a naphthalene moth-azido structure, and is described in the specification of U.S. Patent No. 2,797,213, and U.S. Patent No. 157,416. A substance known in the specification of No. 53-201211686. As an example of a preferred diazonium compound, for example, the following formula (30): [Chem. 44]

[化45] (3 0)

The illustrated brewed diazide sulfonate group, not all of which are simultaneously hydrogen atoms}. Among the naphthoquinonediazidesulfonate groups represented by the above formula (3〇), particularly preferred is 157416.doc -54 - 201211686 The following formula (32): [Chem. 46]

(3 2) wherein, Q is as defined in the above formula (31).芈: 鍈 salt, strontium salt, scaly salt, and diazonium salt, etc., Μ彳 4 4

虱L寺 车乂 is selected from the group consisting of diaryl sulfonium salts, triaryl I salts, and tribasic sulfonium salts (10) salts. The dentate-containing compound may, for example, be a hydrocarbon compound containing a (iv) group, and the like is preferably trichloromethane-based tri-farming. The amount of the photoacid generator to be added is 150 parts by mass, preferably 5 to 3 parts by mass, per 100 parts by mass of the (?) resin. When the blending amount of the photosensitive ray generating agent (c) is 5% by mass or more, the patterning property of the photosensitive resin composition is good, and if it is 50 parts by mass or less, the photosensitive resin composition is cured. The tensile elongation of the film is good and the development residue (scum) of the exposed portion is small. The (D) crosslinking agent may be contained in the photosensitive resin composition of this invention. The crosslinking agent may be a crosslinking agent which can crosslink the (A) resin or the crosslinking agent itself when heat-cured using the convex pattern of the photosensitive resin composition of the present invention, 157416.doc • 55·201211686. Can form a networked road. The crosslinking agent can further enhance the heat and chemical resistance of the cured film formed of the photosensitive resin composition. Examples of the crosslinking agent include ML-26X, ML-24X, ML-236TMP, 4-hydroxymethyl 3M6C, ML-MC, and ML-TBC having one thermal crosslinking group (the above is a trade name, the state Chemical industry (manufactured by the chemical industry), Pa-type benzopyrene (trade name, manufactured by Shikoku Chemical Industries Co., Ltd.), etc., as DM-BI25X-F, 46DMOC, 46DMOIPP, 46DMOEP with two thermal crosslinkable groups (The above is the trade name, Asahi Organic Industry Co., Ltd. ' DML-MBPC ' DML-MBOC > DML-OCHP ' DML-PC, DML-PCHP, DML-PTBP, DML-34X, DML-EP, DML-POP , DML-OC, dipyridyl-Bis-C, dipyridyl-BisOC-P, DML-BisOC-Z, DML-BisOCHP-Z, DML-PFP, DML-PSBP, DML-MB25, DML-MTrisPC , DML-Bis25X-34XL, DML-Bis25X-PCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type , Bm type benzopyrene (the above is the trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), 2,6-dioxadecyl-4-tert-butylphenol, 2,6-didecyloxy Mercapto-p-cresol, 2,6-diethyloxymethyl-p-quinone Or, as a heat-crosslinkable group, TriML-P, TriML-35XL, TriML-TrisCR-HAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc. TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP, TML-HQ, TML-pp_ 157416.doc -56- 201211686 BPF, TML-BPA, ΤΜΟΜ-ΒΡ (above The product name is manufactured by Honshu Chemical Industry Co., Ltd., NIKALAC ΜΧ-280, NIKALAC ΜΧ-270 (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), etc., as HML-TPPHBA with six thermal crosslinkable groups. , HML-TPHAP (above is the trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MW-390, and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

Among these, in the present invention, it is preferred to have at least two heat crosslinkable groups, and particularly preferably 46DMOC, 46DMOEP (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), 〇]\41^ ]^8?(:,〇厘[_]^80(:,〇]\^-OCHP ' DML-PC ' DML-PCHP ' DML-PTBP ' DML-34X ' DML-EP, DML-POP, dihydroxy曱-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), Ba type stupid and ploughing, Bm type stupid and ploughing (above is the trade name, manufactured by Shikoku Chemical Industry Co., Ltd.), 2,6-dimethoxydecyl-4-tert-butylphenol, 2, 6-Dimethoxymethyl-p-nonylphenol, 2,6-diethoxymethyl-p-cresol, TriML-P, TriML-35XL (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.) ), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), TML-BP 'TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP (above is the trade name, the state Chemical Industry (manufacturing), NIKALAC MX-280, NIKALAC MX-270 (above is the trade name, Sanwahua HML-TPPHBA, HML-TPHAP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc. Further, preferably, NIKALAC MX-290, NIKALAC MX-280, NIKALAC 157416.doc -57- 201211686 ΜΧ·270 (above is the trade name, manufactured by Sanhe Chemical Co., Ltd.), B_a type benzoxene well, Bm type benzopyrene well (the above is the trade name, Shikoku Chemical Industry Co., Ltd. )), NIKALAC MW-390, NIKALAC MW1〇〇LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.), etc. Photosensitive resin for various properties other than heat resistance and chemical resistance The blending amount in the case where the composition contains a crosslinking agent is preferably 0.5 to 20 parts by mass, more preferably 2 to 1 part by mass, per 100 parts by mass of the (A) resin. The amount of the compound is 〇5 parts by mass. In the case of the above, it exhibits excellent heat resistance and chemical resistance, and on the other hand, it is excellent in storage stability in the case of 2 parts by mass or less. (E) Organic titanium compound In the photosensitive resin composition of the present invention May contain an organic titanium compound by containing (E) organic titanium compound Further, even when it is hardened at a low temperature of about 25 Å, a photosensitive resin layer excellent in chemical resistance can be formed. In addition, by including both the (B) anthracene derivative and the (E) organic compound in the photosensitive resin composition, it is possible to achieve chemical resistance in addition to the substrate adhesion of the resin layer after curing. Excellent quality. The organic titanium compound which can be used as the (E) organotitanium compound is exemplified by an organic chemical substance bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the (E) organotitanium compound are shown in the following I) to VII;): I) Chelating titanium compound: in which chelate titanium having two or more alkoxy groups is used to obtain a negative photosensitive resin composition. More stable, good pattern, specific examples are bis(triethanolamine) titanium diisopropoxide, 157416.doc •58· 201211686 bis(2,4-pentanedioic acid) di(n-butanol) Titanium, bis(2,4-pentanedioic acid) titanium diisopropylate, bis(tetramethylpimelate) diisopropanol titanium, bis(ethylacetamidineacetic acid) titanium diisopropoxide, and the like. II) a tetra-oxygenated titanium compound: for example, titanium (n-butanol), tetraethanol, tetrakis(2-ethylhexanol), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetraethoxide, tetra Titanium methoxypropoxide, titanium tetradecyl phenol, titanium tetrakis (n-nonanol), titanium tetrakis (n-propanol), titanium tetrastearyl alcohol, tetra [bis{2,2_(allyloxyfluorenyl) Butanol}] Titanium and the like. ΠΙ) Dimochin compound: for example, pentamethylcyclopentadienyl trimethyl titanate, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1Η-pyrrol-1-yl)phenyl)titanium or the like. IV) Monoalkoxy titanium compound: for example, tris(dioctylphosphoric acid) titanium isopropoxide, bis(undecylbenzoic acid) isopropanol, and the like. V) oxytitanium compound: for example, bis(bis(glutaric acid) oxytitanium, bis(tetramethylpimelate)oxytitanium, phthalocyanine oxytitanium or the like. VI) Titanium tetradecylpyruvate compound: for example, titanium tetraethylpyruvate or the like. VII) Titanate coupling agent: for example, isopropyl tris(dodecylbenzenesulfonyl) titanate. Wherein the (Ε) organotitanium compound is a compound selected from at least one of the group consisting of the above 1} chelate ruthenium compound, II) tetra-o-oxy-titanium compound 4, and m) titanocene compound. It is preferable from the viewpoint of achieving better chemical resistance. Particularly preferred is bis(ethyl ethyl acetate) titanium diisopropoxide, titanium tetrakis(n-butanol), and bis(η5·2,4-cyclopenta-1-yl) bis (2,6-di υ·(1Η_ 157416.doc -59. 201211686 ° than 嘻-1-yl) phenyl) Chin. The blending amount of the (E) organotitanium compound is preferably 〇. 5~1 〇 by mass, more preferably 〇1 to 2 parts by mass, based on 1 part by mass of the (A) resin. When the amount is 〇_〇 5 parts by mass or more, it exhibits good heat resistance and chemical resistance. On the other hand, when the amount is less than 1 part by mass, the storage stability is excellent. (F) Other components The photosensitive resin composition of the present invention may further contain components other than the above components (A) to (e). The photosensitive resin composition of the present invention is generally used by dissolving the above-mentioned respective components and any component which is optionally used in a solvent in a solvent to form a photosensitive resin composition in the form of a β lacquer. ) Other ingredients. As the solvent, a polar organic solvent is preferably used in terms of solubility of the (ruthenium) resin. Specific examples thereof include hydrazine, hydrazine-dimethylformamide, hydrazine-methyl-2-pyrrolidone, hydrazine-ethyl-2-pyrrolidone, hydrazine, hydrazine-dimethylacetamide, and dimethyl Sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetylbutyrolactone, tetramethylurea, 1,3-dioxan-2-imidazolidinone, anthracene _cyclohexylpyrrolidone or the like, these may be used singly or in combination of two or more. The solvent may be in the range of, for example, 3 to 15 parts by mass, preferably 100 to 1000 parts by mass, per 100 parts by mass of the (Α) resin, depending on the coating film thickness and viscosity required for the photosensitive resin composition. The scope is used. Further, from the viewpoint of improving the storage stability of the photosensitive resin composition, a solvent containing an alcohol is preferred. The alcohol which can be suitably used is typically an alcohol having an alcoholic hydroxyl group in the molecule and no olefinic double bond. As an example of 157416.doc -60-201211686: methanol, ethanol, n-propanol , isopropanol, n-butyl isobutanol, tributanol and other alkyl alcohols, lactic acid vinegar such as lactic acid, propylene glycol + A, propylene glycol 2 _ test, propylene glycol small acetamidine, C: alcohol I B, propylene glycol (n-propyl, propylene glycol · 2 · (n-propyl hydrazine propylene glycol monoalkyl ethers - ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol, n-propyl) and other monol, 2 - an isobutyric acid, an alcohol such as ethylene glycol or propylene glycol, etc. Among them, preferred are lactic acid g, propylene glycol monoalkyl propylene glycol methyl ether, propylene glycol hydrazine - diethyl ether, and propylene glycol. _1_(n-propyl ether, 2, hydroxyisobutyrate, and ethanol, especially more preferably ethyl acetate), when the solvent contains an alcohol having no olefinic double bond, in the total solvent The content of the alcohol having no olefinic double bond is preferably from 5 to 5% by mass, more preferably from 1 to 30% by mass. When the content of the alcohol is 5% by mass or more, the storage stability of the photosensitive resin composition is improved, and when it is 50% by mass or less, the solubility of the resin (A) is improved. When the photosensitive resin composition of the present invention forms a cured film on a substrate containing copper or a copper alloy, the azole compound can be optionally formulated to suppress discoloration on copper. Examples of the azole compound include 1H-triazole. , 5-mercapto-1H-three-zero, 5-ethyl-1H-trisole, 4,5-dimercapto-1H-tris, 5-phenyl-1H-trisole, 4-third _5_Phenyl-1H_triazole, 5-hydroxyphenyl·1H_triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyldidecylaminoethyl) Oxazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimercapto 157416.doc •61- 201211686 Three saliva, 4'5_diethyl·1Η_tris, benzo 3. Sit, 2♦ methyl 2_ light base * phenyl) benzotriene. Sit, 2·[2_ 经基基_3,5 bis(α,α dimethyl benzyl fluorenyl)benzo-4, 2-(3,5-di-butyl -2- benzoyl benzene Benzotrisole, 2^3·t-butyl-5-methyl-2-pyridylphenyl)benzotrisole, 2_(^_first amyl-2-hydroxyphenyl)benzo Triazole, 2_(2, hydroxy-t-octylphenyl)benzotriazole, hydroxy-p-benzotriazole, tolyltriazole, 5-methyl-1Η-benzotrisene, 4_f-benzotriazine , 4 benzyl benzodiazepine, 5-retayl-1H-benzotriazole, 1H_tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amine Base_1H-tetrazole 'Bu Yinji _ 丨仏 tetrazole and the like. Particularly preferred are toluene triazole, 5-methyl-1H_benzotriazole, and indenyl-1H-benzodiene. sit. Further, these azole compounds may be used alone or in combination of two or more. In the case where the photosensitive resin composition contains the above-mentioned azole compound, the compounding amount is preferably from 1 to 20 parts by mass based on 1 part by mass of the (A) resin, and more preferably from the viewpoint of photosensitivity characteristics. It is 5 to 5 parts by mass. When the amount of the azole compound to be added to 100 parts by mass of the (A) resin is 1.9 parts by mass or more, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, copper or copper is inhibited. The discoloration of the surface of the copper alloy, on the other hand, is excellent in photosensitivity in the case of 20 parts by mass or less. Further, in order to suppress discoloration on the surface of copper, a hindered amine phenol compound can be optionally formulated. The hindered amine phenol compound may, for example, be 2,6-di-tert-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone or octadecyl-3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3_(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4, 4,-methylenebis(2,6-di-third 157416.doc -62- 201211686 butyl phenol), 4,4'-thio-bis(3.methyl-6-tert-butylphenol ), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4- Hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio -diethyl bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis (3,5-di- Tributyl-4-hydroxy-benzoguanamine), 2,2,-methylene-bis(4-mercapto-6-tert-butylphenol), 2,2,-indenylene-double ( 4-ethyl-6-tert-butylphenol), pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris-(3,5- Di-t-butyl-4-hydroxybenzyl)-isocyanuric acid 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, iota, 3,5-tris(3-hydroxy- 2,6-diamidino-4-isopropylbenzyl)-1,3,5-trinol-2,4,6-(1H,3H,5H)-trione, 1,3,5-three (4-tert-butyl-3-hydroxy-2,6-dimercaptobenzyl)-1,3,5-trinol-2,4,6-(111,311,511)-trione, 1 ,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimercaptobenzyl)-1,3,5-three tillage-2,4,6-(1H,3H,5H )-trione, 1,3,5-tris[4-(1-ethylpropyl)-3-hydroxy-2,6-dimercaptobenzyl]-1,3,5-three tillage-2, 4,6_(111,311,511)-trione, 1,3,5-tris[4-triethylindolyl-3-hydroxy-2,6-dimethylbenzyl]-i,3,5 - Three tillage-2,4,6-(1Η,3Η,5Η)-trione, 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-phenylbenzyl)-1 ,3,5-three tillage-2,4,6-(11 €,3 anti511)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5,6 -trimethylbenzyl)-1,3,5-three tillage-2,4,6-(1H,3H,5H)-trione, l,3,5-tris(4-tert-butyl-5 -ethyl-3-hydroxy-2,6-dimethylbenzyl)-l,3,5-tri-p--2,4,6-(lH,3H,5H)-trione, 1,3, 5-tris(4-tert-butyl-6-ethyl-3-hydroxy-2-methylbenzyl )_1,3,5-three 157416.doc •63· 201211686 tillage-2,4,6-(1Η,3Η,5Η)-trione, 1,3,5-tris(4-tert-butyl-6 -ethyl-3-hydroxy-2,5-dimercaptobenzyl)-1,3,5-trinol-2,4,6-(lH,3H,5H)-trione, 1,3,5 -Tris(4_t-butyl-5,6-diethyl-3-hydroxy-2-methylbenzyl)-1,3,5-three tillage-2,4,6-(1Η,3Η, 5Η)-trione' 1,3,5-tris(4-t-butyl-3-hydroxy-2-indolylbenzyl)_1,3,5_three tillage _ 2.4.6- (111,311, 511)-Triketone, 1,3,5-tris(4-t-butyl-3-hydroxy-2,5-(4-tert-butyl-5-ethyl-3-hydroxy-2-indenyl) Benzyl)_ι,3,5-three tillage-2,4,6-(1H,3 Η,5 H)-dione is specifically 'but is not limited thereto. Among these, particularly preferred is 1,3,5-tris(4-t-butyl-3-hydroxy- 2,6-dimercaptobenzyl)-, 3,5-three* well - 2.4.6 - (111,314,511)-trione and the like. The amount of the hindered amine phenol compound is preferably from 0.1 to 20 parts by mass, more preferably from 5 to 10 parts by mass, from the viewpoint of photosensitivity characteristics. When the amount of the hindered amine phenol compound is 1 part by mass or more based on 1 part by mass of the (A) resin, for example, when the photosensitive resin composition of the present invention is formed on copper or a copper alloy, prevention is prevented. The discoloration and corrosion of copper or copper alloy, on the other hand, when the amount is less than 2 parts by mass, the photosensitivity is excellent. The photosensitive resin composition of the present invention may contain a component other than the above components. The preferred component of the component differs depending on, for example, the use of a polyimine precursor or the like as the negative form of the resin (A) or the use of a polycarbazole precursor or the like as a positive type of the resin. In the case where a polyimide precursor is used as a negative type of a resin or the like, a sensitizer can be optionally formulated for the purpose of improving photosensitivity. As the sensitizer, 157416.doc -64-201211686 can be exemplified by: mazilerone, 4,4,-bis(diethylamino)benzophenone, 2,5-bis (4'-diethyl) Aminobenzylidene)cyclopentane, 2,6-bis(4,-diethylaminosuccinyl)cyclohexanone, 2,6-bis(4,-diethylaminobenzylidene)·4 -methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4,_bis(diethylamino)chalcone, p-dimethylaminocincosinone, p-Diammine benzylidene fluorenone, (p-dimethylaminophenyl phenyl) 笨 并 、, 2- (p-dimethylaminophenyl phenyl) benzothiazole, 2- ( P-dimethylaminophenyl vinyl (isophthalazinone), 1,3-bis(4·-diamidinobenzylidene)acetone, iota, 3_bis(4,-diethylamino) Benzyl)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-ethylidene-7-dioxyl coumarin, 3-ethoxycarbonyldiamine Coumarin, oxycarbonyl_7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylamine coumarin, 3-ethoxycarbonyl-7-diethylamine Bean, ice phenyl-indole-ethylethanolamine, N Phenyldiethanolamine, Ν_p-toluene diethanolamine, stupylethanolamine, 4-mercaptodibenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzene Imidazole, 1·phenyl-5-sulfenyltetrasole, 2carbylbenzo(tetra), 2—(p-dimethylaminophenylethyl)benzoxazole, 2-(p-dimethylaminostyrene) Benzobenzothiazole, 2-(p-dimethylaminoethyl)-naphtho(1,2-d)carbazole, 2-(p-dimethylaminobenzyl) styrene, and the like. These may be used singly or in combination of, for example, 2 to 5 types. The amount of the photosensitive resin to be added to the sensitizer for improving the photosensitivity is preferably 〇(10) parts by mass based on 100 parts by mass of the resin. Further, in order to improve the resolution of the raised pattern, the monomer 4 having a photopolymerizable unsaturated bond can be arbitrarily formulated as such (4), and (4) is a free radical by photopolymerization 157416.doc -65-201211686 The (mercapto)acrylic acid compound to be polymerized is not particularly limited to the following, and examples thereof include ethylene glycol or polyethylene glycol such as diethylene glycol dimercapto acrylate or tetraethylene glycol dimethacrylate. Or diacrylates and methacrylates, mono or diacrylates and methacrylates of propylene glycol or polypropylene glycol, mono, di or triacrylates and methacrylates of glycerol, cyclohexane diacrylate and Dimercapto acrylate, i,4-butanediol - propylene vinegar and dimercapto acrylate, 1,6-hexanediol diacrylate and dimethacrylate, neopentyl Alcohol diacrylate and dimethacrylate, bisphenol A mono or diacrylate and methacrylate, benzene trimethacrylate, isobornyl acrylate and methacrylate, acrylamide and Derivatives, methacrylamide and its derivatives, trimethylol propyl Burning diacrylates and mercapto acrylates of glycerol di or triacrylates and methacrylates, pentaerythritol di, tri, or tetraacrylates and methacrylates, and the like A compound such as an ethylene oxide or a propylene oxide adduct. When the photosensitive resin composition contains the photopolymerizable unsaturated bond monomer for improving the resolution of the convex pattern, the amount of the monomer having a photopolymerizable unsaturated bond is relative to the (A) resin. 〇〇 mass parts, preferably 1 to 50 parts by mass. Further, in order to improve the adhesion between the film formed by using the photosensitive resin composition of the present invention and the substrate, the adhesion aid can be optionally formulated. Examples of the subsequent auxiliary agent include γ-aminopropyldimethoxy decane, N—(P-aminoethyl oxime aminopropylmethyldimethoxy decane, glycidoxypropyl hydrazine. Dimethoxyoxane, γ-mercaptopropylmethyldimethoxydecane, 3-methacryl oxime 157416.doc 66- 201211686 oxypropyldimethoxyoxydecane' 3_methacryl醯oxypropyltrimethoxydecane, dimethoxymethyl_3_piperidinylpropyl decane, diethoxy _ 3-glycidoxypropyl decyl decane, N_(3_diethoxy Methyl decyl propyl) butyl quinone imine, N-[3-(triethoxy decyl) propyl] phthalic acid, benzophenone _3, 3i bis (N_ [3_Triethoxydecyl]propyl decylamine)-4,4'-dicapric acid, stupid·triethoxydecylalkyl]propyl decylamine)-2,5-dicarboxylic acid, 3-( Triethoxydecyl)propyl succinic anhydride, \_phenylaminopropyltrimethoxydecane, 3-ureidopropyltrimethoxydecane, 3·ureidopropyltriethoxydecane, 3 - (trialkoxy decyl) propyl succinate and other products such as Shi Xi siu coupling agent and tris(ethyl acetoacetate) aluminum, (Acetylacetonates) aluminum, ethyl acetyl acetate aluminum diisopropylate and other aluminum-based additives followed. Among the above-mentioned auxiliary agents, the use of a decane coupling agent is more preferable in terms of force. In the case where the photosensitive resin composition contains a secondary auxiliary agent, the amount of the auxiliary agent is preferably in the range of 0.5 to 25 parts by mass based on 1 part by mass of the (A) resin. Further, in particular, in order to improve the viscosity and photosensitivity of the photosensitive resin composition during storage in a solvent-containing solution, the thermal polymerization inhibitor can be optionally formulated. As the thermal polymerization inhibitor, hydroquinone, N-nitrosodiphenylamine, p-tert-butyl phthalate, phenol thiophene, N-phenylnaphthylamine, ethylenediaminetetrafene can be used. Acetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-t-butyl-p-methyl phenol, 5-nitroso-8-hydroxyquinoline, Isonitro-2-naphthol, 2-nitroso·ι_naphthol, 2-nitroso-5-(N-ethyl-N-propylpropylamino)benzene, N-Asia; g Schottky-N-phenyl-based amine ammonium salt, N-arylene-N (l-naphthyl) via alkamine salt, and the like. 157416.doc -67-201211686 The amount of the thermal polymerization inhibitor to be blended in the photosensitive resin composition is preferably 5 to 12 parts by mass based on 10 parts by mass of the (A) resin. The scope. On the other hand, when a polycarbazole oxime or the like is used as the positive type of the (A) resin in the photosensitive resin composition of the present invention, a dye used as an additive of the previously photosensitive resin composition may be added as needed. , a surfactant, a bonding aid for the adhesion between the south and the substrate, and the like. When the above-mentioned additive is specifically described, examples of the dye include methyl violet, crystal violet, and malachite green. In addition, examples of the surfactant include a nonionic surfactant including a polyhydric alcohol such as polypropylene glycol or polyoxyethylene lauryl ether or a derivative thereof, for example, Fluorad (trade name, manufactured by Sumitomo 3 River Co., Ltd.), Megafac (trade name: manufactured by Dainippon Ink and Chemicals Co., Ltd.) or a fluorine-based surfactant such as Lumifl〇n (trade name, manufactured by Asahi Glass Co., Ltd.), for example, ΚΡ341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, Chisso Corporation) Manufactured), an organic oxoxane surfactant such as Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.). Examples of the adhesion aid include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, third butyl phenol aldehyde, epoxy decane, epoxy polymer, and the like. Decane coupling agent. Specific preferred examples of the ceramsite coupling agent include, for example, N-phenyl-3-aminopropyltrialkoxydecane, 3-mercaptopropyltrialkoxydecane, 2-(dioxane). Oxidylalkylethyl)pyridine, 3-methacryloxypropyltrialkoxydecane, 3-methylpropenyloxypropyldialkoxyalkylnonane, 3-glycidoxypropane Trilutoxy oxane, 3_glycidoxypropyl 157416.doc • 68 · 201211686 Dialkoxyalkyl decane, 3-aminopropyl trialkoxy decane and 3-aminopropyl one hospital Oxygen: the base group and the anhydride and acid reactants, 3-aminopropyl dialkoxy decane or 3-aminopropyl dialkoxyalkyl decane amine group converted to amine group A An acid ester group or a urea group or the like. In addition, examples of the acid group in the case include a methyl group, an ethyl group, and a butyl group. Examples of the acid anhydride include sodium cis-buthanic acid and phthalic anhydride. Examples of the acid dianhydride include acid dianhydride. : pyromellitic dianhydride, 3,3·,4,4·-benzophenonetetracarboxylic dianhydride, 4,4, oxy-oxo-indolyl phthalic anhydride, etc., as the amino phthalate group Examples thereof include a third butoxycarbonylamino group and the like, and examples of the ureido group include a phenylaminocarbonylamino group and the like. &lt;Manufacturing Method and Semiconductor Device of Hardened Projection Pattern&gt; The present invention provides a method for producing a cured bump pattern, which comprises: (1) applying the photosensitive resin composition of the present invention to a substrate a step of forming a resin layer on the substrate; (2) a step of exposing the resin layer; (3) a step of developing the exposed resin layer to form a raised pattern; and (4) by The raised pattern is subjected to a heat treatment to form a hardened convex pattern. Hereinafter, typical aspects of each step will be described. (1) A step of applying a photosensitive resin composition to a substrate to form a resin layer on the substrate. In the present step, 'coating the photosensitive resin composition of the present invention on a substrate' It is then necessary to dry it to form a resin layer. As the coating method, a method previously applied for coating of a photosensitive resin composition, for example, using a spin coater, a bar coater, a knife coater, a curtain coater, or a screen printing machine can be used. The method of performing coating, 'method of 157416.doc-69-201211686 spray coating using a spray coater, and the like. The coating containing the photosensitive resin composition may be dried as needed. Drying: Method, using air drying, heating and drying using an oven or a heating plate, true: dry and other methods. Specifically, in the case of 二2 °; in the case of air drying or heating and drying, it can be I, and + ^ at 20 〇C~140〇C. Dry for ~1 hour. Axe The above operation forms a resin layer on the substrate. (2) Step of exposing the resin layer In this step, an exposure apparatus such as a contact exposure machine, a mirror projection exposure machine, or a step exposure machine is used, and a mask (10) having a pattern is used. She orsk) or directly (four) ultraviolet light source or the like exposes the resin layer formed as described above. Thereafter, it is also possible to carry out post-exposure baking _) and/or pre-development baking by any combination of temperature and time, in order to increase the photosensitivity and the like. The range of the baking conditions is preferably 40 to 12 (rc, and the time is 10 seconds to 240 seconds 'but the various properties of the photosensitive resin composition of the present invention are not impaired' is not limited to this range. (3) The step of developing the exposed resin layer to form a convex pattern is to "develop and remove the exposed portion or the unexposed portion of the photosensitive resin layer after exposure in this step. In the case where a negative photosensitive resin composition is used. When the polyimide precursor is used as the (A) resin, the unexposed portion is developed and removed, and when a positive photosensitive resin composition is used (for example, a poly-azole precursor is used as the resin). In the case of the case, the exposure portion is removed by development. As a developing method, a development method of a previously known photoresist, such as a whirling spray method, a liquid coating method, a dipping method with ultrasonic treatment, and the like may be selected 157416.doc 201211686 Any method may be used and used. Further, after development, in order to adjust the shape of the convex pattern, etc., it is also possible to perform post-development baking by any combination of temperature and time as needed. It is preferable to use it as a good solvent for the photosensitive resin composition, or a combination of the good solvent and the poor solvent, for example, in the case of insoluble: alkaline water; in the case of the photosensitive resin composition in the gluten solution, as a good solvent 'Preferred to be N-methylpyrrolidone, indole cyclopyrrolidone, N'N-methylammoniumamine, cyclopentanone, cyclohexanone, indole butyrolactone, indomethacin γ-butyrolactone As a poor solvent, it is preferably used in the case of toluene, xylene, methanol ethanol, isopropyl alcohol 'ethyl lactate, propylene glycol methyl ether acetate and water, and /3⁄4 σ good agent and a poor solvent. In the case of the solubility of the polymer in the photosensitive resin composition, the ratio of the poor solvent to the good solvent is preferably adjusted. Alternatively, the solvent may be used in combination of several or more, for example, in another aspect. In the case of a photosensitive resin composition dissolved in a (iv) aqueous solution, the poetic sensible material is an aqueous test solution which is typically a dissolving test compound for transferring a secret polymer. The test compound dissolved in the developer may be inorganic. Test compound or organic test compound The inorganic base compound, for example, j. lithium antimony oxide, sodium hydroquinone, potassium hydroxide, diammonium hydrogen phosphate, dipotassium hydrogen hydride, disodium arsenate, acid chain, sodium citrate, Crushed acid, carbonated surface, lithium, sodium citrate, potassium carbonate, boron lanthanum, sodium borate, potassium borate, and ammonia, etc. Also as the organic base compound, for example, tetradecylhydroquinone 157416.doc •71· 201211686 VII, tetraethyl hydrazine, = methyl acetonate; -r violent ethyl ammonium hydroxide, methylamine, dimethylamine, trimethylamine, hydrazine 7 & Early makeup ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propyl hydrazinium, isopropylamine, diisopropylamine, f-diethylamine , di-f-ethanolamine, ethanolamine, and triethanolamine. Further, a water-soluble organic solvent such as methanol, ethanol, propanol or ethylene glycol, a surfactant, a storage stabilizer, a (tetra) dissolution, or the like may be added to the above-mentioned aqueous test solution as needed. A raised pattern can be formed in the above manner. (4) A step of forming a hardened convex pattern by heat-treating the convex pattern In this step, the convex pattern obtained by the above development is heated to be converted into a hardened convex pattern. As a method of heat hardening, various methods such as a method using a heating plate, a method using an oven, and a method using a temperature-increasing oven capable of setting a temperature program can be selected. The heating can be carried out, for example, at si8 (rc~4 〇 (rc is carried out for 30 minutes to 5 hours. The ambient gas in the case of heat curing can be used as an air, and an inert gas such as nitrogen or argon can also be used. &lt;Semiconductor device&gt; The present invention further provides a semiconductor device which has a hardened convex pattern obtained by the above-described method for producing a hardened convex pattern of the present invention. The present invention also provides a semiconductor device comprising a substrate as a semiconductor element and a cured bump pattern of a resin formed on the substrate by the method of manufacturing the cured bump pattern. Further, the present invention is also applicable to a method of manufacturing a semiconductor device using a semiconductor device as a substrate and a method of manufacturing the above-described cured bump pattern as a part of the steps. The semiconductor device of the present invention can be manufactured by a method of forming a hardened bump pattern formed by the above-described hardened bump pattern manufacturing method as a surface protective film, an interlayer insulating film, and an insulating film for rewiring. A protective film for a flip chip device, a protective film for a semiconductor device having a bump structure, or the like is combined with a known method for manufacturing a semiconductor device. The photosensitive resin composition of the present invention can be used for applications such as interlayer insulation of a multilayer circuit, a protective layer of a flexible copper drop plate, a solder resist film, and a liquid crystal alignment film, in addition to the above-described semiconductor device. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited thereto. In the examples, comparative examples and production examples, the physical properties of the photosensitive resin composition were measured and evaluated according to the following methods. (1) Weight average molecular weight The weight average molecular weight (Mw) of each resin was measured by gel permeation chromatography (standard polystyrene conversion). The column used for the measurement is the brand name "Shodex 8〇5M/8〇6M series" manufactured by Showa Denko Electric Co., Ltd., and the standard monodisperse polystyrene is selected from the brand name "Hiro" STANDARD SM manufactured by Showa Denko Electric Co., Ltd. -105", the developing solvent was N_methyl_2_pyrrolidinium, and the detector was sold under the trade name "Sh〇dex 930" manufactured by Showa Denko. (2) Copper discoloration test The photosensitive resin composition was spin-coated on a steel substrate and dried to form a coating film having a thickness of 30 μm as a resin layer. Then, in the case of the photosensitive resin composition which is not dissolved in the alkaline aqueous solution, the use of cyclopentanone is carried out using a 157416.doc •73·201211686 camera (D-SPIN636 type, manufactured by Otsuka Screen Manufacturing Co., Ltd., Japan) The spray coating formed on the wafer is spray-developed and washed with propylene glycol and vinegar vinegar, thereby completely dissolving the coating film. In the case of the photosensitive resin composition dissolved in an alkaline aqueous solution, the entire surface was irradiated with an energy of 500 mJ/cm by a parallel light ray alignment exposure machine (PLA-501FA, manufactured by Canon, Japan). 'Using an in-progress developer (AZ300MIF developer, 2.38 mass% aqueous solution of tetramethylammonium hydroxide) manufactured by AZ Electronic Materials Co., Ltd., dip-developing with a developing machine, and rinsing with pure water, thereby completely dissolving the coating film . The copper substrate after dissolution was evaluated according to the following criteria: "Best": No discoloration of the copper substrate was observed by visual observation or observation with an optical microscope of 200 times; "Good": No discoloration of the copper substrate was observed by visual observation. When observed by an optical microscope at 200 times, a slight discoloration of the copper substrate was observed; "slightly better": no discoloration of the copper substrate was observed by visual observation, and the discoloration of the copper substrate was observed when observed under an optical microscope 2 times; "poor" : The discoloration of the copper substrate to a serious extent was visually observed. (3) Copper adhesion test (number of substrate adhesion grids) The photosensitive resin composition was spin-coated on a copper substrate, dried, and a coating film having a thickness of 17 μm was formed into a photosensitive resin layer, and then a temperature-increasing pattern was used. A curing oven (VF-2000 type, manufactured by Koyo Lindberg Co., Ltd., Japan) was heat-treated (cured) at 200 ° C for 1 hour under a nitrogen atmosphere, followed by heat treatment (curing) at 250 ° C for 2 hours, thereby obtaining 1〇μπι thick hardened resin coating film. For the cured film, the adhesion characteristics between the copper substrate/hardened resin coating film were evaluated based on the following criteria in accordance with the JIS Κ 5600-5-6 standard 157416.doc • 74·201211686 cross-cutting method. "Best": The number of lattices of the cured resin coating film adhered to the substrate is 100. "Good": The number of lattices of the cured resin coating film adhered to the substrate is 80 to 99. "Slightly better": The number of lattices of the cured resin coating film adhered to the substrate is 5 〇 to 79. "Slightly poor": The number of lattices of the cured resin coating film adhered to the substrate is 20 to 49. "Unsatisfactory": The number of lattices of the hardened resin coating film adhered to the substrate is less than 2 inches. (4) Chemical resistance test (formation of a convex pattern by a negative photosensitive resin) Spin-coated photosensitive resin composition on a ruthenium wafer (manufactured by Kyodo International Co., Ltd.) with a 6-inch nitride film The resultant was dried to form a coating film having a thickness of 17 μm to form a photosensitive resin layer. Exposure was carried out by irradiating energy to the coating film at 200 mJ/cm 2 using a mask attached to the test pattern by a ghi line stepper (prisma_ghi, manufactured by uitratech Co., Ltd.). Then, the coating film formed on the wafer was spray-developed using a developing machine (D-SPIN636 type, 曰本, manufactured by Dainippon Screen Manufacturing Co., Ltd.) using cyclopentanone, and washed with propylene glycol methyl ether acetate. The unexposed portion was removed by development to obtain a convex pattern of the resin. Using a temperature-programming type curing oven (VF_2000 type, manufactured by K〇y〇Lindberg, Japan), heat treatment of a wafer having a raised pattern at 200 C under a nitrogen atmosphere of 157416.doc -75 - 201211686 Hours, then 250. (: The heat treatment was carried out for 2 hours, whereby a hardened convex pattern of a resin of 1 〇μηι thick was obtained on the circle on the day after the nitride film was attached. (Formation of a convex pattern by a positive photosensitive resin) The photosensitive resin composition was spin-coated on a 6-inch nitride film (manufactured by Ky〇d〇interna U〇nai Co., Ltd.) to form a coating film as a photosensitive resin layer. The film was exposed to light by irradiating the coating film at 3 〇〇mJ/cm 2 by an i-line stepper (NSR2005i8A, manufactured by Nikon Co., Ltd.), and then a 2.38 mass% aqueous solution of tetramethylammonium hydroxide was used. The coating film formed on the wafer was spray-developed by a developing machine (D_spi N636 type, manufactured by Otsuka Screen Manufacturing Co., Ltd., Japan), rinsed with pure water, and the exposed portion was developed and removed to obtain a convex pattern of the resin. Using a temperature-programming type curing oven (VF_2〇〇〇 type, manufactured by K〇y〇Lindberg, Japan), the wafer in which the raised pattern was formed was heat-treated under a nitrogen atmosphere, followed by 32 Torr. With nitrogen attached A hardened convex pattern of a resin of 1 μm thick is obtained on the wafer of the film. (Evaluation of chemical resistance of the hardened convex pattern by the negative photosensitive resin) The hardened convex pattern obtained is contained in the hydroxide In a solution of 1% by mass of potassium, 39% by mass of 3-methoxy-3-methyl-1-butanol, and 60% by mass of dimercaptoarylene, it was 100. (: 1 hour under dipping. Washing and air drying) Thereafter, the resin coating film was evaluated according to the following criteria by film thickness measurement and observation under an optical microscope: "Best": the film thickness after coating after the impregnation was ±1% with respect to the film thickness before the coating film There is no crack in the inside. "Good": The film thickness of the coating film changes within ±3% without cracking. 157416.doc -76· 201211686 Shape. "Poor": film thickness changes over ±3 % or cracking occurred. (Evaluation of chemical resistance of hardened convex pattern by positive photosensitive resin) The obtained hardened convex pattern was applied to ST-44 (trade name, manufactured by ATMI) 8 (dip for 5 minutes under TC. After washing and air drying, by film thickness measurement and observation under light microscope The resin coating film was evaluated according to the following criteria: "Best j: The film thickness after the coating film with respect to the coating film before the impregnation was ±1% or less, and no crack occurred." "Good": The film thickness of the coating film changes within ±3% without cracking. "Unsatisfactory": The film thickness changes by more than ±3% or cracks occur. <Production Example 1> ((A) Synthesis of polymer A as a precursor of poly-bromide) 1551 g of 4,4'-oxybis-p-dibenzoic acid dianhydride (〇DpA) was placed in a separable flask of 2 μ capacity and placed in a thiol group. 131.2 g of 2-hydroxyethyl acrylate (HEMA) and 4 μm of γ-butyrolactone were stirred at room temperature, and 81·5 g of pyridine was added while stirring to obtain a reaction mixture. After the end of the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours. Then, under ice cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 18 〇ml of γ-butyrolactone was stirred while stirring, and it took 40 knives to add π to the reaction mixture. Then, while stirring, it takes 60 knives to add 4,4'-diaminodibenzophenone (DADpE) 93 〇g suspended in a crucible from 350 ml. After further stirring at room temperature for 2 hours, 3 〇ml of ethanol was added and stirred for 1 hour, followed by addition of γ-butyrol vinegar 400 m by filtration of 157416.doc -77-201211686, and the reaction mixture was taken out to form the sediment. , the reaction solution was obtained. The obtained reaction liquid was added to an ethanol of 31 to form a sediment containing a coarse aggregate. The resulting crude polymer was separated by filtration and dissolved in four gas hexanes 1.51 to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 1 of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and vacuum-dried to obtain a powdery polymer (Polymer A). The molecular weight of the polymer A was determined by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000. <Production Example 2> (Synthesis of Polymer b as (A) Polyimine Precursor) In addition to the use of 3,3,4,4--biphenyltetradecanoic acid dianhydride (BPDA) 147.1 g instead of the production example A polymer B was obtained in the same manner as in the method described in Production Example 1 except that 4,4'-oxybisphthalic acid dianhydride (ODPA) was used in an amount of 155 μg. The molecular weight of the polymer B was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000. &lt;Production Example 3&gt; (Synthesis of Polymer C as (A) Polyimine Precursor) 155.1 g of 4,4'-oxydiphthalic dianhydride (〇dpa) was placed in a capacity of 21 In a separable flask, put 2-hydroxyethyl methacrylate (HEMA) 13 1.2 g and γ-butyrolactone 400 m b and mix at room temperature. Add pyridine 8 1 ·5 g while stirring. , the reaction mixture was obtained. After the end of the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours. Then, under ice cooling, a solution obtained by dissolving 206.3 g of dicyclohexylcarbodiimide (DCC) in 180 ml of γ-butyrolactone while stirring was added to the reaction mixture for 40 minutes, and then, It took 6 minutes to stir and add 4 4,-diaminodiphenyl ether (DADPE) 93.0 g to be suspended in γ-butane 157416.doc • 78· 201211686 ester 350 ml. After further stirring at room temperature for 2 hours, 8 g of aza-adenine was added and scrambled for 2 hours, followed by addition of γ-butyrolactone 4, and the precipitate formed in the reaction mixture was taken out by filtration to obtain The reaction solution. The obtained reaction liquid was added to ethanol of 31 to form a precipitate containing a crude polymer. The resulting crude polymer was separated by filtration and dissolved in tetrahydrofuran 1.5 1 to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 1 of water to precipitate a polymer, and the obtained precipitate was separated by filtration, and vacuum-dried to obtain a powdery polymer (polymer c). The molecular weight of the polymer c was determined by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 22,000. <Production Example 4> (Synthesis of Polymer d as (A) Polyimine Precursor) In addition to the use of 3,3',4,4'-biphenyltetraphthalic acid dianhydride (BPDA) 1471 § instead of the production example The reaction was carried out in the same manner as in the method described in the above Production Example 3 except that 3,4'-oxydiphthalic dianhydride (〇DPA) was 155 1 g to obtain a polymer D. The amount of the polymer D was measured by gel permeation chromatography (standard polystyrene conversion). As a result, the weight average molecular weight (Mw) was 24,000. &lt;Production Example 5&gt; (Synthesis of Polymer e as Polyamide) (Synthesis of Phthalate Compound Sealing Agent AIPA-MO) 5-Aminoisophthalate was placed in a separable flask having a capacity of 5 1 Formic acid (hereinafter abbreviated as AIPA} 543_5 g, N-mercapto-2-pyrrolidone 1700 g, and mixed and stirred, and heated to 5 (rc in a water bath), in which the isocyanate is added by using a dropping funnel. Methyl propylene methoxyethyl ester 512.0 g (3.3 m 〇l) diluted by γ-butane s 5 〇〇g 'continued at 5 (rc under 2 hours left 157416.doc -79-201211686 right Using low molecular weight gel permeation chromatography (hereinafter, referred to as low molecular weight GPC), the reaction solution was put into 15 liters of ion-exchanged water after the end of the reaction (the disappearance of 5-amino phthalic acid). The mixture was stirred and allowed to stand, and the crystallized precipitate of the reaction product was awaited and separated by filtration, and after appropriate washing with water, vacuum drying was carried out under vacuum for 48 hours, thereby obtaining an amine group and an equivalent of 5-aminoisophthalic acid. AipA_MO which acts on the isocyanate group of 2-methylpropenyloxyethyl cyanate. The purity of the low molecular weight Gpc of AIP-MO obtained is about 1% by mass. (Synthesis of Polymer E) The obtained ΑΙρΑ_Μ〇100.89 g (0,3 mol), pyridine 71.2 g (〇9 m〇1), GBL were placed in a separable flask of a capacity of 2 1 . 4〇〇g, and mixed 'cooled to the ice bath. In which, under the cooling of the ice bath, fb costs about 20 minutes to add dicyclohexylcarbodiimide (Dcc) 125. 〇g (0.606 Mol) dissolved and diluted in GBL 125 g, and then spent 2 minutes to add 4,4 · bis (4-aminophenoxy)biphenyl {to D, recorded as BAPB} 103.16 g (0.28 Mol) Dissolve mNMP 168. Use ice-cold to maintain less than 5 C and mix for 3 hours, then remove the ice bath and stir at room temperature for 5 hours. Remove the sediment formed in the reaction mixture by filtration to obtain the reaction. To the obtained reaction solution, a mixture of 840 g of water and 560 g of isopropyl alcohol was added dropwise, and the polymer separated and precipitated was redissolved in NMP 650 g. The obtained crude polymer solution was added dropwise to 5 1 . In the water, the polymer was precipitated, and after the obtained precipitate was separated, it was vacuum dried to obtain a powdery polymer (Polymer E). By gel permeation chromatography (standard polystyrene) 1574l6.doc • 80 · 201211686 molecular weight measurement of polymer E 'resulting weight-average molecular weight (mw) was 34,700 square &lt;Production Example 6&gt; (Synthesis of Polymer F as (A) Polycarbazole Precursor) In a separable flask having a capacity of 31, 22 bis (3-amine) at room temperature (25 Torr) 183.1 g of keto-4-hydroxyphenyl)-hexafluoropropane, N,N-metemethamine (DMAc) 64 〇.9 g, and 63.3 g of pyridine were mixed and stirred to prepare a solution of the same sentence. Using a dropping funnel, 118.0 g of 4,4,-dibenzofluorene gas was dissolved in 354 g of diethylene glycol dimethyl ether (DmdG). At this time, the separable flask was used. Cooling in a water bath of ~20 ° C. The time required for the dropwise addition is 40 minutes, and the temperature of the reaction liquid is at most 30 ° C. After 3 hours from the end of the dropwise addition, 1,2 -cyclohexyl bis-alkali anhydride 30.8 is added to the reaction liquid. g (〇.2 mol), stirred at room temperature for 15 hours, using a few cyclohexyl guanamine groups to seal 99% of the total amine end group of the polymer chain. The reaction rate at this time can be achieved by using high-performance liquid phase Chromatography (HPLC) traces the remaining amount of the 1,2-cyclohexyldicarboxylic anhydride to be easily calculated. Thereafter, the above reaction solution is added dropwise to 2 L of water under high-speed stirring to obtain a polymer. The precipitated 'recovered and recovered' is appropriately washed with water, dehydrated, and then vacuum dried, and the crude polybenzoxazole having a weight average molecular weight of 9'000 (polystyrene equivalent) measured by a gel permeation chromatography (GPC) method is known. Precursor. The crude polybenzophenone obtained in the above. After the precursor is redissolved in γ-butyrolactone (GBL), it is treated with a cation exchange resin and an anion exchange resin. After the solution was poured into ion-exchanged water, the precipitated polymer was separated by filtration, washed with water, and vacuum dried to obtain a purified polybenzazole precursor F (polymer F). 157416.doc 201211686 <Production Example 7> (Synthesis of Polymer G as (A) Polyimine) Mounted in a separable four-necked flask made of glass with a stirrer made of Teflon (registered trademark) Cooling tube of the water separator. The flask was placed in an oil bath while stirring with nitrogen gas. 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by ciariant Japan) was added (below) Called ΒΑΡ) 72·28 g (280 m Ear), 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) (hereinafter referred to as MCTC) 70 29 g (266 mmol), γ-butyrolactone 254.6 g, toluene 60 g, and stirred at 1 rpm for 4 hours at room temperature, then added 5_norbornene 2,3-dicarboxylic anhydride (Tokyo 4.6 g (28 mmol) manufactured by Chemical Industry Co., Ltd. was heated and stirred at 100 rpm for 8 hours while being passed through a nitrogen atmosphere at a bath temperature of 50 °C. Thereafter, the mixture was heated to a bath temperature of 180 ° C, and heated and stirred at 1 Torr for 2 hours. The distillate component of toluene and water during the reaction was removed. After the hydrazine imidization reaction is completed, it is returned to room temperature. Thereafter, the above reaction solution was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dehydrated, and then vacuum dried to obtain gel permeation chromatography (Gpc). A crude polyimine having a weight average molecular weight of 23,000 (in terms of polystyrene) as determined by the method. &lt;Example 1&gt; Using a polymer A and B, a negative photosensitive resin composition was prepared by the following method, and the prepared photosensitive resin composition was evaluated. Polymer A5〇g&amp;B5〇g (equivalent to tree 157416.doc -82- 201211686 lipid) and 8-azadenine (equivalent to (B) anthracene derivative) 0.2 g as a polyimide precursor , 1-phenyl _ i, 2-propanedione 2 - (o-ethoxycarbonyl)- hydrazine (described as "pD 〇" in Table 1) (corresponding to (C) sensitizer) 4 g, 1, 3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-three tillage-2,4,6-(1Η,3Η,5Η) - Triketone U g, N-phenyldiethanolamine 10 g, decyloxyguanidinated urea resin (MX-290) (corresponding to (D) crosslinker) 4 g, tetraethylene glycol dimercapto acrylate 8 g, N-[3-(triethoxy oxalate) propyl] o-benzidine 1.5 g, and 2-nitros naphthol quinone. 5 g - and dissolved in N-containing A mixed solvent of 80 g of methyl-2-pyrrolidone (hereinafter referred to as NMP) and 20 g of ethyl lactate. A negative photosensitive resin composition was prepared by further adding a small amount of the above mixed solvent to adjust the viscosity of the obtained solution to about 35 poise. When the negative photosensitive resin composition was evaluated by the above method, the evaluation of copper discoloration was evaluated as "best", the evaluation of copper adhesion was "best", and the evaluation of chemical resistance was "best". &lt;Examples 2, 3&gt; Example 1 is taken as the (B) anthracene derivative in the present invention.

The same as in Example 1. &lt;Example 4&gt;

The resin group of the resin was subjected to the same procedure as in Example 1 to prepare an evaluation of negative photosensitive. Evaluation of copper discoloration 157416.doc • 83· 201211686 The result of chemical resistance was “good”, and the result of evaluation of copper adhesion was “the best evaluation result was the same as in Example 1. &lt;Example 5&gt; In the present invention, the amount of the 8-azagyo 7 of the „A „A ^ ^ θ organism is changed to the composition shown in Table i, and the negative sensitization composition is prepared by the character FX, and is the same as in the first embodiment. The evaluation of the cream is like this! + h. The evaluation results were the same as in Example 1. &lt;Example 6&gt; According to the composition shown in Table 1, 8_azaguanine mi 7 was used instead of the 8-aza "呤" as the derivative of (B) t in the present invention, and the preparation was negative. The photosensitive resin composition of the type was evaluated in the same manner as in Example 1. The evaluation results were the same as in Example 1. 11 ', 〇 <Example 7> Adenine was used instead of the Example according to the composition shown in Table 1. In the present invention, the (B) anthraquinone derivative (8-azadenine) was prepared, and the negative photosensitive resin composition was prepared, and the same evaluation as in the above (4) was carried out. The result of evaluating the copper discoloration was "good", and the evaluation was performed. The result is "good." The evaluation results of the chemical resistance were the same as those in the examples. &lt;Example 8&gt; According to the composition shown in Table 1, N,N-dimethyladenine was used instead of the 8-azepine as the (B) anthracene derivative of the present invention, and a negative preparation was prepared. The photosensitive resin composition of the type was evaluated in the same manner as in Example 饧. The result of #饧铜色色 is "good", and the result of evaluating copper is "slightly better". The evaluation results of the chemical resistance were the same as those of the examples. 157416.doc -84 - 201211686 &lt;Example 9&gt; According to the composition shown in Table 1, hypoxanthine was used instead of the 8-azadenine which is the (B) anthracene derivative of the present invention, and was prepared. The negative photosensitive resin composition was evaluated in the same manner as in Example 。. The result of evaluating copper color change was "slightly better", and the result of evaluating copper adhesion was "slightly better". The evaluation results of chemical resistance were the same as in Example 1. &lt;Example 10&gt; The same as Example i except that bis(ethylacetylacetic acid) titanium diisopropoxide (E1)0 ig as the (E) organotitanium compound was further added to the composition of Example 1. In this manner, a negative photosensitive resin composition was prepared. As a result of the evaluation of the chemical resistance, the change in the film thickness of the film was within ±1%, and no crack was observed, which was "best". The other evaluation results are the same as those of the embodiment. &lt;Example 11&gt; A negative photosensitive resin was prepared in the same manner as in Example w except that tetrakis(n-butanol)titanium (E2)Gl g as the (8) organotitanium compound was further added to the composition of Example i. combination. As a result of the evaluation of the chemical resistance, the film thickness of the film was changed to within ±丨%, and the crack was not observed in the door, which was the "best". The other evaluation results are the same as those of the embodiment. &lt;Example 12&gt; In addition to 5 in the composition of the solid addition 1, bis(η -2,4-d-pentyl bis(2,6-difluoro- 3 辄.(4) small group) as (8) organotitanium compound was further added. Phenyl) and (4), in the same manner as in the implementation _ (4) 贞 (4) The first chemical resin composition 1 line of chemical resistance evaluation results, the film thickness change of the film is within ± 1%, nor observed To the crack, it is "best". Others 157416.doc -85- 201211686 The evaluation results are the same as in the first embodiment. &lt;Example 13&gt; A negative photosensitive film was prepared in the same manner as in Example 1 except that the polymer A 100 g was used as the (A) resin in the present invention instead of the polymer A 50 g and the polymer 3 5 〇§ The resin composition was evaluated in the same manner as in Example. The evaluation results were the same as in Example 10. <Example 14> In addition to the use of the polymer E 1 〇〇 g as the resin in the present invention (4) instead of the polymer A The negative photosensitive resin composition was produced in the same manner as in Example i except for 50 g and the polymer B, and the same evaluation as in Example 。 was carried out. The parity result was the same as in Example 1. <Example 15> The prepared photosensitive resin composition was evaluated by using the polymer F and preparing a positive photosensitive resin composition by the following method. The polymer resin composition was evaluated as a poly. (Α) resin) and the following formula (33): [Chem. 47]

Ch3-c-ch3 (33) Φ 将 The secret of the secret (4) 77% silk two money _4 box 6|photosensitive 157416.doc •86- 201211686 Diazo brewing compound (made by Toyo Synthetic Co., Ltd. (c) sensitizer) (described as "Cl" in the table) 20 g, 8-azadenine (corresponding to (B) hydrazine derivative) 0.2 g, 3-butoxycarbonylaminopropyl 6 g of triethoxylate was dissolved in 1 μg of γ-butyrolactone (as a solvent). The positive photosensitive resin composition was prepared by further adding a small amount of γ-butyrolactone to adjust the viscosity of the obtained solution to about 2 Torr. According to the above method sf., the positive-type photosensitive resin composition was evaluated, and as a result, the evaluation of the discoloration of the steel was "best", the evaluation of the copper adhesion was "best", and the evaluation of the chemical resistance was "better". <Example 16> A positive photosensitive resin composition was prepared in the same manner as in Example 15 except that the polymer G 1 〇〇g was used as the resin (A) in the present invention instead of the polymer F 100 g. The same evaluation as in Example 15. The evaluation results were the same as in Example 15. &lt;Comparative Example 1&gt; Negative photosensitiveness was prepared in the same manner as in Example 除 except that benzotriazole was added in place of 8-azadenine in the composition shown in Table 1 in the composition shown in Table 1. The resin composition was subjected to the same evaluation as in Example 。. According to the above method, it is coated on a ruthenium wafer and a copper substrate, and dried, exposed, "negative ~ and heat-treated, thereby obtaining a chemical resistant flat of 4 Å of the polyimide film obtained by the above method", but The (B) 嗓+ derivative of the present invention is not included, so the evaluation of copper discoloration is "poor", and the evaluation of copper adhesion is "poor tip" 〇 &lt;Comparative Example 2&gt; 157416.doc -87 - 201211686 The benzotriazole was not formulated in the composition of Comparative Example 1, and the polymer C 50 g and the polymer D 5〇g were used as the (A) polyimine precursor in the present invention instead of the polymer A 50 g and polymerization. A negative photosensitive resin composition was prepared in the same manner as in Comparative Example 1, except that the object b was 50 g, and the same evaluation as in Example 1 was carried out. "Coated on a silicon wafer and a copper substrate according to the above method, and dried and exposed. , development, and heat treatment, the chemical resistance of the polyimide film obtained by the evaluation was "good", but the evaluation of copper discoloration was "poor", and the evaluation of copper adhesion was "slightly better". . 157416.doc • 88- 201211686

157416.doc Comparative Example 2 〇〇〇〇〇 inch 〇〇 ο ο ο ο ο ο ο Poor slightly poor: 30 Comparative Example 1 〇〇〇〇〇〇〇ο ο ο ο ΓΊ ο ο ο ο Poor Slightly poor: 30 Example 16 〇〇〇〇〇〇100 〇&lt;Ν &lt;ζ&gt; ο ο ο ο ο ο ο ο Best and Best: 100 Example 15 〇〇〇〇〇§ 〇〇rs d ο ο ο ο ο ο ο ο 1 Best: 100 Example 14 〇〇〇〇100 〇〇rf 〇&lt;N c&gt; ο ο ο ο ο ο ο ο Best Best: 100 Example 13 § 〇〇 〇〇〇〇 〇 S S S S 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施〇cs o ο ο ο ο ο ο 5 ο Best: 1 (8) Embodiment 10 〇〇〇〇〇〇 &lt;N ο ο ο ο ο 5 ο ο Best ig 铒 - Best Embodiment 9 沄〇〇〇〇 〇〇o ο ο ο (Ν ο ο ο ο ο slightly better: 50 Example 8 〇〇〇〇〇〇 o ο ο (Ν ο ο ο ο ο ο slightly better: 55 Example 7 〇〇〇〇〇〇o ο (Ν ο ο ο ο ο ο ο 00 实施 Example 6 〇〇〇〇〇〇o ΓΜ ο ο ο ο ο ο ο ο 啦 Best: 100 Example 5 〇 〇 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο 实施 3 〇〇〇〇〇 〇 〇 〇 ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο Example 1 〇〇〇〇〇 〇 ο ο ο ο ο ο ο Best and Best: 100 Polymer A Polymer B Polymer C Polymer D i Polymer E Polymer F Polymer G PDO C 8-Nitrogen Adenine 8·azepine adenine, Ν-dimethyladenine, jaundice, stupid and triazolium a copper discoloration test can be Ϊ 俤 俤 耐 耐 耐 89 89 89 89 89 89 89 89 89 89 89 89 Usability] The photosensitive resin composition of the present invention can be preferably used for, for example, semiconducting Field of the electrical device, the multilayer wiring board or the like / electronic materials useful for manufacturing a photosensitive materials. 157416.doc -90-

Claims (1)

201211686 VII. Patent Application Range: 1. A photosensitive resin composition containing the following components: (A) selected from the group consisting of polylysine as a polyimine precursor, polyglycolate, and can be polymerized. The oxazole precursor polyhydroxy decylamine, polyamine amide 'amine, polyamine, polyamidimide, polyimide, polybenzopyrene, polybenzophenone, and poly At least one resin of the group consisting of benzothiazepine: 100 parts by mass; (Β) anthracene derivative: 0.01 to 10 parts by mass based on 1 part by mass of the (Α) resin; and (C) The sensitizer is a photosensitive resin composition according to claim 1, wherein the (Α) resin is selected from the group consisting of the following formula: (1): [Chemical 1] ΗΙΝI Υ1 - ΗΙΝI OMC \ / one Ri〇—C&quot; ιι Ο C-OR2 ιι Ο Π1 {中中' 有机β4 organic base, 1 is a 2-valent organic base, 2~150 Integer, and the heart is separated by a hydrogen atom, respectively. (2): S I574l6.doc 201211686 [Chemical 2] ~fCH2^7°--CC=&lt;^ (2) (wherein, R3, &amp; and RS are each independently an organic group of a hydrogen atom or a carbon number of 3, and are called an integer of 2 to 10), or a saturated carbon number of 1 to 4 A polyimine precursor having a structure represented by an aliphatic group] having the following formula (3): [Chemical 3] (3) In the formula, X2 is a trivalent organic group having a carbon number of 6 to 15, and γ2 is a 2-valent organic group having a carbon number of 6 to 35, and is of the same structure, or may have a plurality of structures, and I is a carbon number. a polyamine having a structure of 3 to 20 having an organic group 'having at least one radical polymerizable unsaturated bond group and Π 2 being an integer of 1 to 1000} having the following formula (4): ] ΟΗ — — —CO—X3—CONH-Y3—ΝΗ— —CO—X4—CONH — Y broad nh OH—n3——where Υ3 is a tetravalent organic group with carbon atoms 'Y4, x3, and χ4 Separately, it is a divalent organic group having two or more carbon atoms, and is 157416.doc •2- (4) 201211686 integer, 114 is an integer from 0 to 500, 113/(113+114)&gt; 5, and contains ns dihydroxydiamine units of \ and Y3 and the arrangement order of ... and the diammonium units containing no limitation of the structure of the polyoxazole precursor, and having the structure The general formula (5): [Chemical 5] Ο 〇 ΛΝ ΛΝ ΛΝ γ Ν Ν Υ ο ο ο R R R R R R R 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Organic base, R7 and Rs Each of which independently represents an organic group having at least one group selected from a phenolic hydroxyl group, a sulfonic acid group or a thiol group, and ns is an integer of 3 to 2 Å, and is represented by an integer represented by an integer of 0 to 10} At least one resin of the group consisting of polyimine. 3. The photosensitive resin composition of claim 1, wherein the (b) hydrazine derivative is selected from the group consisting of the following formula (6): In the formula, R9 is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or an alkyl group or an aromatic group having 1 to 10 carbon atoms, and R1() is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 6 carbon atoms. a compound represented by a hydroxy 'hydroxyalkyl group or an amine group which may be substituted with a decyl group or an aromatic group having 1 to 1 〇 157416.doc 201211686, the following general formula (7): [Chemical 7] Ο Ri Rl2 Rl3 (7) {wherein the ruler 11 is a hydrogen atom, a halogen atom, a trans group, an amine group or a C 1 or 10 alkyl group or an aromatic group, and Rlz and R13 are each independently a hydrogen atom, a trans group, a hydroxyl group. a compound represented by an alkyl group or an alkyl group or an aromatic group having a carbon number of biO, the following general formula (8): [Chemical Formula 8] , Ν (8) WV, Ν', amine or carbon number, _ atom, {wherein, R14 is a hydrogen atom, a halogen atom, a hydroxyl group of 1 to 10 alkyl or an aromatic group, and Ri5 is hydrogen month a compound represented by an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a hydroxyalkyl group or an amine group which may be substituted with an alkyl group or an aromatic group of 1 carbon atom, and the following general formula (9): &quot; [ 9] Ο Rie 157416.doc (9) 201211686 {wherein, Rie is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or an alkyl group or an aromatic group having a carbon number of 1 to ί, and Rn&amp;Ri8 are independently a hydrogen atom, a hydroxyl group, At least one anthracene derivative of a group consisting of a hydroxyalkyl group or a compound represented by an alkyl group or an aromatic group of carbon number iqo. 4. The photosensitive resin composition of claim 2, wherein the (B) hydrazine derivative is selected from the following formula (6): [Chem. 6] In the formula, R9 is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or a alkyl group or an aromatic group having 1 to 10 carbon atoms, and r1g is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group. a compound represented by a hydroxyalkyl group or an amine group which may be substituted by an alkyl group or an aromatic group of a carbon number] (the following formula (7) · [Chemical 7] In the formula, Ru is a hydrogen atom, a halogen atom, a trans group, an amine group or an alkyl group or an aromatic group having a carbon number of 1 to 10, and RuKR! 3 is independently a hydrogen atom, a hydroxyl group, a hydroxyalkyl group or a carbon number of 1 ～10 alkyl or aromatic group) Compound represented by the following formula (8): 157416.doc 201211686 [Chem. 8] In the formula, R14 is a hydrogen atom, a _ atom, a thiol group, an alkyl group or an aromatic group having an amino group of 1 to 10, and Ris is a halogen atom of a hydrogen atom, an alkoxy group having a carbon number of 1 to 6, a hydroxyl group, or a hydroxyl group. a compound represented by an alkyl group or an amine group which may be substituted with an alkyl group or an aromatic group having 1 to 7 carbon atoms, and a compound of the following formula (9): I Rl8 (9) {wherein, Rie is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or an alkyl group or an aromatic group having a carbon number of ι~ιο, and Ri7&amp;Ris are independently a hydrogen atom, a meridine, and a trans group. At least one anthracene derivative of the group consisting of a compound represented by an alkyl group or an alkyl group or an aromatic group. 5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (B) anthracene derivative is selected from the group consisting of the following formula (1〇): (10) I574I6.doc • 6 - 201211686 {wherein, Rb is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or an alkyl group having 1 to 10 carbon atoms or an aromatic group}, and the following formula ( 11): [Chem. 11] 0 In the formula, R2 is a compound represented by a hydrogen atom, a hydroxyalkyl group or an alkyl group of carbon number (7), and the following formula (12): [Chemical 12] In the formula, R: n is a hydrogen atom, a halogen atom, a hydroxyl group, an amine group or a compound having a carbon number of 1 to 10 or an aromatic group, and the following formula (13): Ο In the formula, R22 is at least one anthracene derivative of a group consisting of a compound represented by a hydrogen atom, a hydroxyalkyl group or an alkyl group having a carbon number of 丨~1〇. 6. The photosensitive resin composition according to any one of claims 1 to 4, wherein the (B) anthracene derivative is a compound selected from the group consisting of the above formula (12), and 157416.doc 201211686 (the above formula ( 13) at least one compound of the group consisting of the compounds shown. 7. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (D) a crosslinking agent: 〇5 to 2 parts by mass based on 1 part by mass of the above (A) resin . 8. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (E) an organic titanium compound: 0.05 to 10 parts by mass based on 1 part by mass of the above (A) resin . 9. The photosensitive resin composition of claim 8, wherein the (E) organic compound is at least one compound selected from the group consisting of a titanium chelate compound, a tetraalkoxy titanium compound, and a titanocene compound. . 10. A method of producing a hardened convex pattern, comprising: (1) forming a photosensitive property on a substrate by applying a photosensitive resin composition as claimed in any one of claims 1 to 9 to a substrate; a step of exposing the photosensitive resin layer; (2) a step of exposing the photosensitive resin layer; (3) a step of developing the exposed photosensitive resin layer to form a raised pattern; and (4) by using the protrusion The pattern is subjected to a heat treatment to form a hardened convex pattern. 11. The method of claim 10, wherein the substrate is formed of copper or a copper alloy. A semiconductor device having a hardened bump pattern obtained by the method of manufacturing the item (7) or the crucible. 157416.doc •8- 201211686 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the invention: (none) 157416.doc