TW201011465A - Photosensitive resin composition - Google Patents

Abstract

Disclosed is a photosensitive resin composition characterized by containing 1-50 parts by mass of (B) a photoacid generator and 1-40 parts by mass of (C) a compound represented by general formula (2) (wherein D1 represents at least one group selected from the group consisting of a hydrogen atom, alkyl groups having 1-6 carbon atoms, alkenyl groups and crosslinkable organic groups; M1 represents a group selected from the group consisting of -CH2-, -O- and -S-; Z1 represents a divalent organic group; n1 represents an integer of 0-4; and when there are a plurality of D1's, the D1's may be the same as or different from each other), per 100 parts by mass of (A) an alkaline aqueous solution-soluble polymer having a hydroxyamide structure represented by general formula (1) (wherein X1 represents a tetravalent organic group having at least 2 carbon atoms; Y1 represents a divalent organic group having at least 2 carbon atoms; and m1 represents an integer of 1-1000).

Description

[Technical Field] The present invention relates to a positive photosensitive resin composition which is used as a surface protective film or an interlayer insulating film of a semiconductor device as a precursor to a thermal resin, and the use of the positive photosensitive resin composition A method for producing a heat-resistant cured embossed pattern of a photosensitive resin composition, and a semiconductor-device having the cured embossed pattern.

[Previously, the surface protective film of the semiconductor device and the interlayer insulating film of the prior art have been widely used as a polyanilin resin having excellent heat resistance, electrical properties, and mechanical properties. Currently, the polyimine resin is usually provided in the form of a photosensitive polyimide intermediate composition. In the process of manufacturing a semiconductor device, the precursor composition is applied onto a substrate such as a germanium wafer, patterned by active light, developed, and further subjected to thermal imidization treatment or the like, whereby the precursor composition can be easily formed. It is a surface protective film that is part of the semiconductor device, or a layer of ruthenium. Therefore, the manufacturing process of the semiconductor device using the photosensitive polyimide intermediate precursor composition has a characteristic that the step of the step can be greatly shortened compared with the previous manufacturing process using the non-photosensitive polyimide intermediate composition. The manufacturing process must be patterned by the lithography method after forming a surface protective film or the like. The 'photosensitive polyimide precursor composition must use N-methyl-2- in its development step. An organic solvent such as pirolidinone has been used as a developing solution, and the industry is looking for a countermeasure against organic solvents due to the increasing environmental problems in recent years. Therefore, various proposals have been made recently for a heat-resistant photosensitive resin material which can be developed in an alkaline aqueous solution in the same manner as a photoresist. In the following, Patent Document 1 and Patent Document 2 disclose the following methods, and in recent years, attention has been paid to an aqueous solution of a hydroxypolyamine which is an aqueous solution of a heat-resistant resin after curing, such as polybenzoxazole (hereinafter also referred to as polybenzoxazole). The "PBO" precursor is mixed with a photoacid generator such as a naphthoquinone diazide compound, and the PBO precursor composition obtained by mixing is used as a positive photosensitive resin composition. The development mechanism of the bismuth-type photosensitive resin composition is as follows: the naphthoquinonediazide compound and the pB ruthenium precursor in the unexposed portion have a small dissolution rate in an alkaline aqueous solution, and by exposure, The photosensitive diazonium compound chemically changes to become a thoracic carboxylic acid compound, and the dissolution rate of the exposed portion in the alkaline aqueous solution is increased. By using the difference in the dissolution rate between the exposed portion and the unexposed portion in the developer, an embossed pattern including the unexposed portion can be produced. The above PBO precursor composition can form a positive relief pattern by exposure and development using an aqueous alkaline solution. Further, the PBO film which is formed by heat treatment to form a carbazole ring has the same thermosetting film property as the polyimide film, and thus the PBO rigid-drive composition is used as a ruthenium instead of an organic solvent. The material of the composition has received attention. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. SHO63162 JP-A-2005-134743 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-134743 [Draft of the Invention] [Problems to be Solved by the Invention] However, 'PBO Precursor Composition and Photosensitive Polyimine Precursor The composition of the composition has a lower sensitivity due to the problem associated with the absorption wavelength of the sensitizer, and therefore has a higher sensitivity composition. Further, since these cured films are used for a surface protective film or the like, it is necessary to have good thermal/mechanical properties or good adhesion to a substrate such as Si which is a base. Patent Document 3 discloses a heat resistant resin composition containing a compound having a three-pill frame and/or a vinyl group and a PBO-based repellent resin as essential components. Further, although a method is proposed in which a hardening organic compound having at least one brewing imine group and having two or more unsaturated groups and/or an epoxy group in the molecule is used, and having a relationship with the main chain A method for improving sensitivity and thermomechanical properties by using a bisallyl-diadiimide compound or a bis-butyleneimine compound or the like in a resin bond in which a hetero atom-bonded carbonyl group is used (patent) Document 4) 'But in the case where the polymer structure has no anthranium group, it does not exhibit the function as a photoresist. Therefore, it is presumed that the development mechanism is not the same, and the sensitivity improvement effect is also insufficient. Further, the resin which becomes the binder does not change as cyclized as the PBO precursor, so >4 is Tg (glass transiti 〇 I1 teniperature, glass transition temperature) does not change 'and hardly affects the shape of the solidification. The problem to be solved by the present invention is to provide a positive photosensitive resin composition which is excellent in pattern shape after curing of a resin and has high sensitivity and high adhesion and positive lithographic performance, and a hardened relief pattern using the composition is used. A method of fabricating a method of using the hardened embossed pattern. [Means for Solving the Problem] The present inventors have found that a photosensitive resin composition capable of solving the above problems can be obtained by combining a specific compound with a heat-resistant aqueous solution-soluble polymer having a specific structure, and the present invention has been completed. That is, the present invention is as follows. The π] photosensitive resin composition is characterized in that it contains (B) a photoacid generator with respect to 100 parts by mass of an alkaline aqueous solution-soluble polymer having a hydroxyguanamine structure represented by the following formula (1).丨~50 parts by mass, (c) the following. 40 parts by mass of the compound represented by the formula (2): [Chemical Formula 1] / 〇H Ο 〇v {wherein X is 4 having at least 2 carbon atoms The valence organic group, Υι is a divalent organic group having at least 2 carbon atoms, and is called! ~〗 〇〇〇 整数 integer);

In the formula, the functional group having at least one selected from the group consisting of a hydrogen atom, an alkyl group of a carbon number 6, a dilute group, and a crosslinkable organic group, and % is selected from -CH2·, _0- and The base of the group consisting of _S_, the heart is a divalent organic group, 140356.doc 201011465 1 is an integer of 〇~4, and when there are plural 〇丨, a plurality of 丨玎 are the same or different}. [2] The photosensitive resin composition according to the above [1], wherein the photoacid generator is a compound having a naphthoquinonediazide structure. [3] The photosensitive resin composition according to the above [1] or [2] wherein (c) the compound represented by the formula (2) is selected from the group consisting of the compounds represented by the formula (3). : [Chemical 3]

The photosensitive resin composition of any one of the above-mentioned [1] to [3], wherein (A) an alkali aqueous solution soluble polymer having a hydroxyguanamine structure represented by the general formula (1) It has a structure represented by the following formula (4): [Chemical 4]

In the formula, X3 represents a group selected from the group consisting of a single bond and the following formula (5): [Chemical 5] 〇 »ch3 cf3 (5) Ο ? 一 C C C C C C C C C C C C C C C C C C C C C C C C C C C C At least one of the constituents of the constituent group, [2 and independently represent no gas atom or sulfhydryl group, and L4 represents a hydrogen atom, a sulfhydryl group or a hydroxyl group}. [5] The photosensitive resin composition according to any one of the above [1] to [4] wherein (A) is an aqueous alkaline solution having a hydroxyguanamine structure represented by the formula 41). The end of the substance is selected from the group consisting of the following general formula (6): [Chem. 6]

140356.doc (6) 201011465 {In the formula, the 'L5 table is not selected from the group consisting of „, 1, and the group consisting of CH2-, 〇-, and -S-, and L6 represents a hydrogen atom or an alkyl group. (6) A method of producing a photosensitive resin layer comprising the photosensitive resin composition according to any one of the above (1) to (5); (7) via a photomask; a step of exposing or directly irradiating light, an electron beam or an ion beam with actinic rays, (7) a step of eluting or removing the exposed portion or the irradiated portion; and a step of heat-treating the obtained embossed pattern. It has a hardened embossed pattern obtained by the method of the above [6]. [Effects of the Invention] According to the present invention, the pattern shape is excellent when the resin is cured, and the sensitivity is sensitive and dense. A positive photosensitive resin composition for a positive southern lithography performance, a method for producing a cured embossed pattern using the positive photosensitive resin composition, and a semiconductor device having the cured embossed pattern. [Embodiment] <Photosensitive Tree (Four composition) The components constituting the photosensitive resin composition are specifically described below. (A) The alkaline aqueous solution-soluble polymer is (A) having the base polymer as the positive photosensitive resin composition of the present invention. In the case of the alkaline aqueous solution-soluble polymer having a hydroxyguanamine structure represented by the above formula (1), the structure thereof is not particularly limited, and may have a structure represented by the following formula (10) in order to control alkali solubility. From the viewpoint of the transparency of the i-line region and the solubility of the exposed portion in the test developer, it is preferable to have a structure of the following formula (4).

In the formula, Χι is a tetravalent organic group having at least 2 carbon atoms, 丫丨 is a divalent organic group having at least 2 carbon atoms, and 1111 is an integer of 1 to 1000} [Chemical 8]

9» 0 〇 X]-NH—C_ Yj—〇 OH

Ο Ο nh-x2-nh-~c-y2-c

In the formula, X is a tetravalent organic group having at least two carbon atoms, 丫! And 1 are each independently a divalent organic group having at least 2 carbon atoms, which is called! ~ 〇 〇 整数 整数 叱 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数 整数

140356.doc •10- 201011465 stands for hydrogen L2 and L3 are respectively methyl or via

At least one structure of the group, Li, atom or f group, and l4 represents a hydrogen atom, [Chemical 10]

Furthermore, it is good to choose [Chemical 11]

(8) Among them, particularly preferred is the following formula (9). [化 12]

(9) First, a structure having a PBO precursor which is a unit including 乂1 and 丫1 among the structures represented by the above formula (1) and the above formula (7) will be described. The 140356.doc -11 - 201011465 dihydroxydiamine unit has a polycondensation of a dicarboxylic acid having a structure of Yl(COOH)2 and a bisaminophenol having a structure of Χ(ΝΗ2)2(ΟΗ)2. The structure. The two groups of amine groups and hydroxyl groups of the bisaminophenol are in the ortho position to each other, and the hydroxypolyamine is heated to about 250 to 400. (:: Closed-loop, converted to polyphenylene as a heat-resistant resin, oxazolium. Χι is preferably a tetravalent organic group having two or more carbon atoms of 30 or less. Υι preferably has two or more 30 The divalent organic group of the following carbon atoms is called the range of (7) (8), preferably in the range of 2 to 100, more preferably in the range of 3 to 6 Å. In the structure represented by the above formula (1) The hydroxypolyamine may optionally have a diammonium unit of the above formula (7). The diamine unit has a diamine having a structure of xdNH2)2 and a diacid having a structure of Y2(COOH)2. A structure obtained by polycondensation. It is better to be in the range of 1 to 5 inches, and more preferably in the range of 1 to 10. In the structure represented by the above formula (1), the higher the ratio of the above-mentioned dihydroxydiamine unit in the polyamide, the higher the solubility in the alkaline aqueous solution used as the developer, and thus the πιΑη The value of ^+ιη2) is better than the above 'better is 0.7 or more, and the best is 〇.8 or more. Examples of the bisaminophenol having a ΧΚΝΗΟ/ΟΗ) 2 structure include, for example, .3,3′-di-diphenylaniline, 3,3′-diamino-4 4,4′-di-based stupid, 4 , 4'-diamino-3,3'-di-biphenyl, 3,3'-diamino-4,4,-dihydroxydiphenyl milling, 4,4'-diamino-3 , 3,-dihydroxydiphenyl sulfone, bis(3-aminohydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3- Amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, bis(4-amino-3-hydroxyphenyl)methane, 2 , 2-bis(4-amine 140356.doc •12- 201011465 -3-hydroxyphenyl)propane, 4,4,-diamino-3,3,-dihydroxybenzophenone, 3,3' -diamino-4,4i-dihydroxybenzophenone, 4,4,-diamino-3,3,-dihydroxydiphenyl ether, 3,3,-diamino-4 4,4' _Dihydroxydiphenyl ether, hydrazine, 4-diamino-2,5-dihydroxy stupid, I% diamine 2,4-dihydroxybenzene, hydrazine, 3•diamino _ 4,6- Dihydroxybenzene and the like. These bisaminophenols may be used singly or in combination. Particularly preferred among these bisaminophenols having a KNHJWOH) 2 structure is that the oxime is an aromatic group selected from the group consisting of the following. [Chem. 13]

Further, as a compound of the structure of Χι(ΝΗ2)2(ΟΗ)2, it is also possible to use a diamine having two groups of amidoxime bonds and a phenolic hydroxyl group in the ortho position in the molecule (hereinafter referred to as "the intrinsic PBO precursor" The diamine of the structure of the structure is, for example, obtained by reacting two molecules of wall-based benzoic acid with the above-mentioned bisaminophenol having a structure of Xi(NH 2 ) 2 (〇H) 2 to be reduced by the following Diamine represented by the formula: [Chemical Formula 14] Η2Ν

CCKNH, HO〆 zNH-Cχί ΌΗ

ΝΗ 2 140356.doc • 13- 201011465 wherein X4 is a tetravalent organic group having at least two carbon atoms, preferably selected from the group consisting of the organic groups represented by the above X! At least one organic group}. As another method for obtaining a diamine having a pB 〇 precursor structure in a molecule, it is also possible to obtain a 2-molecular nitroaminophenol and a dioxane having a structure of Y3(c〇cl) 2 to be reduced. A method of a diamine represented by the following formula: [Chem. 15]

In the formula, Y3 is preferably a divalent organic group having at least two or more carbon atoms, and is preferably at least one organic group selected from the group consisting of an organic group represented by Y1 to be described later. Examples of the diamine having a structure of X2(NH2)2 include an aromatic diamine and an anthracene diamine. Examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine, 2,4-nonylphenylenediamine, 3,3'-diaminodiphenyl ether, and 3,4,diamine. Diphenyl ether, 4,4'-diaminodiphenyl ether, 3,3,-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4,_ Diaminodiphenylsulfone, 3,3,-diaminodiphenylphosphonium 7,4,4,-diaminodiphenylphosphonium 6,34,diaminodiphenylnonane, 4, 4'-Diaminodiphenyl sulfide, 3,3,-diaminodiphenyl ketone, 4'4'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone , 2,2,_Diamine U0356.doc •14- 201011465 Phenylphenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, hydrazine, 3_bis (3-aminobenzene) Oxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4-mercapto-2,4-bis(4- Aminophenyl)-1-pentyl, 4-mercapto-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimercapto-4 -amino group) phenyl, imino-di-p-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-mercapto-2,4-bis(4-amine Phenyl)pentane , 5 (or 6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindan, bis(p-aminophenyl)phosphine oxide, 4,4,_di Amino azobenzene, 4,4'-diaminodiphenylurea, 4,4,bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-amino) Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy) Phenyl]benzophenone, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 4,4'-bis[4-(α,α-dimercapto-4-amine Benzyl)phenoxy]diphenyl fluorenone, 4,41_bis[4_(〇1,〇1_dimethyl-4-aminobenzyl)phenoxy]diphenyl milling, 4,4,- Diaminobiphenyl, 4,4'-diaminobenzhydryl, phenylindanediamine, 3,3,·dimethoxy-4,4,-diaminobiphenyl, 3,3 '-Dimercapto-4,4,-diaminobiphenyl, o-toluidine oxime, 2,2-bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxybenzene) Base, hard, bis(4-aminophenoxyphenyl) sulfide, 1,4-(4-aminophenoxyphenyl)benzene, 1,3-(4-aminophenoxyphenyl) Benzene, 9,9-bis(4-aminophenyl)anthracene, 4,4'-di(3-amino-phenyl) Diphenyl hard, 4,4'-diaminobenzimidamide, etc. and the hydrogen atom of the aromatic nucleus of the aromatic diamine are selected from the group consisting of a gas atom, a fluorine atom, a bromine atom, a methyl group, and a ruthenium atom. A compound obtained by substituting at least one group or atom of a group consisting of a cyano group, a cyano group, and a phenyl group. Further, in order to improve the adhesion to the substrate, the quinone diamine may be selected from a part or all of the diamine having the x2(NH 2 ) 2 structure, and as an example, it may be listed as 140356.doc -15· 201011465: double 4-aminophenyl)didecyldecane, bis(4-aminophenyl)tetradecyloxane, bis(4-aminophenyl)tetramethyldioxane, bis(γ-amine Propyl)tetramethyldioxane, 1,4-bis(γ-aminopropyldiindenyl)benzene, bis(4-aminobutyl)tetramethyldioxane, double Aminopropyl)tetraphenyldioxane, and the like. Examples of the dicarboxylic acid having a structure of Yi(COOH) 2 and Y2(COOH) 2 include diaryl acids in which Υι and Y2 are each an aromatic group or an aliphatic group selected from the following. [Chemistry 16]

(wherein 'A' represents a divalent group selected from the group consisting of _Ch2-, _〇_, _s_, _s〇2_, _c〇, NHCO-, _c(CF3)2-, and a single bond, respectively Represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an unsaturated group, and a halogen atom, and k represents an integer of 〇~4} [Chem. 17]

140356.doc 201011465 {wherein, Ls, L9 and L10 each independently represent a hydrogen atom or a methyl group, and ^丨 represents a ruthenium atom, a methyl group or a thiol group.) In the above group, the mechanical properties of the obtained resin film are good. In other words, L8, L9, L1() and L&quot; are the hydrogen atoms. As representative compounds of the dicarboxylic acid having a tricyclodecane skeleton, bis(carboxy)tricyclo[5,2,1,02,6]nonane can be cited. This compound can be carried out according to the synthesis method of Production Example A of Japanese Patent No. 538-11-11, or the example of Japanese Patent No. 2002-5〇4891! The synthesis method or the synthesis method of Synthesis Example 2 of Japanese Patent Laid-Open Publication No. Hei 09-15846. However, in these methods, since heavy metals are used as the oxidizing agent, the heavy metal is not used, and the following production method is more preferable. That is, tricyclo(5,2,1,decene)decanedioxan (manufactured by Tokyo Chemical Industry Co., Ltd., catalogue N〇τ〇85〇) is dissolved in acetonitrile or the like 'addition 2,2,6,6-four A catalyst such as a piperidine-i-oxyl radical (hereinafter also referred to as "TEMPO") is used to adjust the pH value by using dihydrogen hydride or sodium monohydrogen phosphate. By performing φ oxidation 'and purifying', bis(carboxy)tricyclo[5,2,1,02,6]nonane as a target compound can be produced. • Further, a dicarboxylic acid compound having a structure other than the above-mentioned compound (11) can be obtained by a fluorenylcyclopentadiene dimer (manufactured by Tokyo Chemical Industry Co., Ltd.). 0920), 1-methyldicyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd., catalogue Ν〇·Μ0910) or 1-hydroxydicyclopentadiene (Tokyo Chemical Industry Manufacturing Catalogue N0.HO684) as raw material, using j. 〇rg. Chem,, 45, 3527 (1980), after hydrogen bromide or hydrogen chloride is added to the unsaturated bond of the above starting material, according to j. Am. Chem. 140356.doc .17- 201011465 S已知e·, 95, 249 (1973), adding carbon monoxide and water' to introduce two hydroxyindoles into the skeleton of tricyclo[mo2,6]nonane as a synthesis methyl group The method, in addition to the above, can also be used to add 9-bad bicyclic (3,3,1) decane to an unsaturated state by using a method known from J. Am. Chem. Soc., 91, 2150 (1969). After forming an intermediate at the bond site, it is reacted with carbon monoxide, and then reduced by UAlH(OCH3)3 to produce a dihydroxyindole matrix. The dimethylhydrazine group of the dimethyl group obtained by the above method is similarly oxidized according to the method described in the case of obtaining bis(carboxy)tricyclo[5,2,1,〇2'6]nonane. Thereby, the target dicarboxylic acid can be obtained. Further, a derivative of 5-aminoisophthalic acid may be used in part or all of the above dibasic acid having a structure of 丫1(0:〇〇11)2 and 丫2((:〇〇11)2. Specific compounds which are reacted with 5-aminoisophthalic acid in order to obtain the derivative include 5-norfosene-2,3-diphthalic anhydride and exo-3,6-epoxy- 1,2,3,6-tetrahydrophthalic anhydride, 3-ethynyl-1,2-phthalic acid liver, 4-ethynyl-1,2-phthalic anhydride, cis_4 _Cyclohexene-indole, 2 dicapric acid needle, 1-cyclohexene-1,2-diphthalic anhydride, maleic anhydride 'methyl cis-butane dianhydride, fluorenylene succinic anhydride, Nea Methyltetrahydrophthalic acid, decyl endoiyltetrahydrophthalic anhydride, methyltetrahydrophthalic acid liver, allyl succinic anhydride, isocyanoethyl methacrylate , 3_Isopropyl-α,α-dimethylbenzyl isocyanate, 3_cyclohexene, j-helium, 2_bite, 曱 〇, croton, cinnamyl, propylene Helium, propane gas, propyne helium, butyne chloro, thiophene-2-ethoxime, styrene sulphur, methacrylic acid Glycidyl ester, allyl glycidol, shouting, gas grim 140356.doc -18- 201011465 oxime ester, ethyl formate, n-propyl chloroformate, isopropyl methacrylate, isobutyl chloroformate, chlorodecanoic acid 2-Ethyl decyl ester, second butyl phthalate benzyl chlorate, 2-ethylhexyl chloroformate, allyl carbureate, phenyl benzoate, chlorinated acid 2, 2, 2- Tri-equivalent ethyl ester, 2-butoxyethyl formate, nitrobenzyl carbazate, p-methoxybenzyl chloroantimonate, isodecyl benzyl formate, biphenyl isopropyl benzyl chlorate , 2-tert-butoxycarbonyl-oxyimino-2-phenylphenylacetonitrile, S-t-butoxycarbonyl-4,6-dimethyl-thiopyrimidine, dibutyl phthalate, N-B Oxycarbonyl phthalimide, ethyl dithizone, helium, benzamidine, sulfonium sulfonate, sulfonium sulfonium, acenaphthyl chloride, diphenyl methane, three Mercapto gas decane, hexamethyldioxane, N,0-bis(dimethylalkylalkyl)acetamide, bis(trimethyldecyl)trifluoroacetamide, (N,N-dimethyl Amino)trimethylsulfanyl, (dimethylamino)trimethylsulfonium monomethyl Shi Xizhuo diphenyl service, bis (trimethyl sulphate) urea, phenyl isocyanate, n-butyl isocyanate, n-octadecyl isocyanate, o-tolyl isocyanate, 1,2-phthalic anhydride, cis-hydrazine, 2-cyclohexanedicarboxylic anhydride, and glutaric acid needle. Further, as a structure having Y1(c〇〇H)2 and Y2(CO〇H)2 As the dicarboxylic acid, a dicarboxylic acid obtained by ring-opening a tetracarboxylic dianhydride with a monool or a monoamine may be used. Examples of the monool herein include decyl alcohol, ethanol, propanol and iso Examples of the monoamine include butylamine, butanol, butanol, benzyl alcohol, and the like. Examples of the monocarboxylic acid dianhydride include compounds represented by the following chemical formulas. 140356.doc •19- 201011465 [Chem. 18]

In the formula, A2 represents a divalent group selected from the group consisting of _Ch2_, _〇, -s-, -S02-, _C0·, '-NHCO-, and -C(CF3)2-). As another method, tetracarboxylic dianhydride may be reacted with a bisaminophenol or a diamine, and the resulting carboxylic acid residue may be esterified or aminated with a monool or a monoamine. Further, trimellitic chloride may be reacted with bisaminophenol to form a tetracarboxylic acid dianhydride, which may be opened as a monocarboxylic acid in the same manner as the above tetracarboxylic dianhydride. As the tetracarboxylic dianhydride obtained herein, a chemical formula represented by the following chemical formula can be cited: [Chem. 19]

In the formula, X5 represents a divalent organic group represented by X1(OH)2(NH_)2, and X1 has the same meaning as in the above formula (1)}. As a method for synthesizing the polyglycolic acid and the bis-amino stupid (diamine) by condensing the mercaptoamine, the diamine can be exemplified by using diterpenic acid and sulfite to obtain the diamine. A method in which a phenyl benzophenone (diamine) functions; 140356.doc • 20- 201011465 A method in which an acid and a bisaminobenzene (diamine) are condensed by a dicyclohexyl carbon (four) enthalpy. In the method of using the g-based carbon-quinone imine, the hydroxybenzotriazole can also be used at the same time.

It is also preferred that the above-mentioned base polyamine having a repeating unit represented by the formula (1) is used for blocking the terminal group with an organic group (hereinafter referred to as "blocking group"), and the base is used. In the polycondensation of a brewing amine, when a di-lowering acid component is used in excess of the molar amount compared to the sum of the diaminobenzene component and the diamine component, it is preferred to use an amine group or a wire as a capping agent. Base compound. Examples of the compound include stilbene, ethyl hexylamine, norfloxacin, butylamine, propargylamine, ethanol, propargyl alcohol, stearyl alcohol, hydroxyethyl methacrylate, and hydroxyethyl acrylate. On the other hand, when the sum of the bisaminophenol component and the diamine component is used in excess of the number of moles compared to the dicarboxylic acid component, it is preferred to use an acid anhydride, a carboxylic acid, a helium or an isocyanate group. A compound that blocks the base. Examples of the compound include, for example, benzamidine gas, norbornene dicaprate liver, norbornenecarboxylic acid, ethynyl phthalic anhydride, glutaric anhydride, cis-succinic anhydride, phthalic anhydride, Cyclohexanedicarboxylic anhydride, methylcyclohexanedicarboxylic acid needle, % hexamethylene carboxylic acid needle, ▼-based methacrylic acid methyl propyl ethoxylate, styrene isocyanate, methylsulfonate and p-toluenesulfonate Chlorine, etc. It is also irrelevant to use only the above-mentioned base polyamine in the base polymer of the photosensitive resin composition, and it is also possible to cyclize and condense the dihydrogen diamine and the aromatic diamine having a dilute hydroxyl group. The obtained polyquinone imine structure having a phenolic hydroxyl group is copolymerized as needed. As a tetras-acid dianhydride in the synthesis of a polyethylenimine containing a phenolic hydroxyl group, from the viewpoint of solvent solubility, a preferred oxime is selected from the group consisting of aroma having a carbon number of 8 to 36.

3'3 ’4,4 - 联五笨(qUinqUe_phenyi) tetracarboxylic acid II

4,4'-diphthalic acid dianhydride, it's ethyl _4,4,_diphthalic dianhydride, 1,3,trimethylene-4,4,-di-phthalic acid Acid dianhydride, hydrazine, 4_tetramethylene _ 4,4'-diphthalic dianhydride, 1&gt;5_pentamethylene _4,4,_diphthalic acid, one needle, double 3,4-di-reinylphenyl)ether two-needle, thio- 4,4,-diphthalic phthalic anhydride 'sulfonyl _4,4'-diphthalic dianhydride, 込^ double ^'Dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 14-bis(3,4-dicarboxyphenoxy)phthalic anhydride, l53 _bis[2_(34-dicarboxyphenyl)_2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)·2-propyl]benzene di-field, double [ 3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4_(3,4-dicarboxyphenoxy)phenyl]decane dianhydride, 2,2-bis[3-( 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, double (3,4·2 Carboxyphenoxy)dimethylhydrazine dianhydride, l,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldioxanane dianhydride, 2,3 6,7-naphthalenetetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid 140356.doc • 22- 201011465 dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride , 2,3,6,7-decanetetracarboxylic dianhydride, 1,2,7,8-phenanthrenecarboxylic acid dianhydride, ethyltetracarboxylic dianhydride, 1,2,3,4-butane tetradecanoic acid Dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentane tetracarboxylic acid two-needle, cyclohexene _1,2,3,4_tetracarboxylic acid, traitor, ring 2,4,5·tetracarboxylic dianhydride, 3,3,4,4-d-d-decyl tetracarboxylic acid di-hepatic, alkyl _4,4′-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride , fluorenylene 4,4,-bis(cyclohexane·1,2-dicarboxylic acid) dianhydride, 込2-extended ethyl _4,4′ bis (cyclohexan-1,2-diindole) Acid) dianhydride, 1.1-ethylene-4,4'-bis(cyclohexane-1,2-didecanoic acid) dianhydride, 2,2-propylene _ 4,4,-bis (cyclohexyl) Alkane-1,2.dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1.2-dicarboxylic acid) dianhydride, thio- 4,4·-bis(cyclohexane-1, 2-dicarboxylic acid) dianhydride, sulphate-4,4'-bis(cyclohexan-1,2-dicarboxylic acid) dihepatic, bicyclo[2,2,2] xin_7_ dilute-2,3,5 ,6-tetradecanoic acid dianhydride, internal type [1S, 5R, 6R Bu 3_oxa Cyclo[3,2,1]octane-2,4-dione-6-spiro-3,-(tetrahydrofuran-2,5,-dione), 4_(2,5-dioxotetrahydrofuran-3- Base)·1,2,3,4-tetrahydronaphthalene_1,2-dicarboxylic anhydride, ethylene glycol·bis(3,4-monoformate heparaphenyl), etc., of which 5_( 2,5-dioxotetrahydro-3-furanyl)_3_methyl-cyclohexene_U2_dicarboxylic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4- Dicarboxyphenyl)sulfone dianhydride, 4,4'-(4,4-isopropylidene monophenoxy) bis(phthalic anhydride), of which, in view of the transparency of the i-line of a mercury lamp More preferably, in the aspect of solubility and photosensitivity in an aqueous alkaline solution, 5_(2,5-dioxotetrahydro-3-(furanyl)-3-methyl-cyclohexene core, 〉2 Formic acid _, double (3, 4_ two county phenyl) Mystery II · Liver. The monoamine which is used in the quinone imine unit having a phenolic hydroxyl group and which has a phenolic property, is selected from the above diamines (n=2) biting 140356.doc • 23- 201011465 In the group of non-promising diamines (n=〇), or 2,4-diaminophenol (n=l) may be mentioned. Among them, 2,2-bis(3-amino-4-hydroxyphenyl)propane is more preferable from the viewpoint of high photosensitivity of the resin composition. The dehydration condensation reaction in the synthesis of a quinone imine unit having a phenolic hydroxyl group can be carried out according to the method disclosed in, for example, International Publication No. 01/034679, by the above tetracarboxylic dianhydride and the above phenolic diamine in acid. Or heated to 3 Torr in the presence of a base catalyst. (:~220. (:, preferably 170. (: ~200.): As an acid catalyst, an inorganic acid such as sulfuric acid or the like which is usually used in the manufacture of polyimine can be used. An organic acid such as benzenesulfonic acid, γ-valerol and η-pyridine can also be used. As the base catalyst, pyridine, triethylamine, dimethylaminopyridine or 18-diazabicyclo can be used. 4,0) undecene-7,1,3,5,7-tetraazabicyclo (3,3,1,1,3,7) anthracene, triethylenediamine, etc. Further In the following method, a polycondensation catalyst or the like is not particularly added, and the temperature of the reaction liquid is maintained at a temperature higher than the temperature at which the hydrazine imidization reaction is carried out, and the water generated by the dehydration reaction is discharged by using a solvent azeotropy with water or the like. To the outside of the reaction system, the hydrazine imidation dehydration condensation reaction is completed. As the reaction solvent for performing the dehydration condensation reaction, in addition to the benzene which is a solvent for azeotroping water, it is preferably used to make it soluble. a polar organic solvent in which an aqueous solution of an aqueous solution is dissolved in an aqueous alkaline solution. As the polar solvent, γ-butyrolactone or N-methyl can be used. Pyrrolidone, dimethyl decylamine, dimethyl acetamide, tetramethyl gland, cyclobutyl or the like. In the production of polyimine, in addition to the above phenolic diamine, the above non-phenol is optionally required The diamine is copolymerized, whereby it can also be controlled in the solubility or physical properties in an alkaline aqueous solution. U0356.doc •24- 201011465 _Further than the use of more than two kinds of acid reading two or more than two In the case of a diamine or a non-(tetra)diamine, it is also possible to form a desired copolymer condensation condensate by a secondary reaction. Further, when a raw material of three or more components is added, a raw material may be simultaneously added to the anti-I system. To form a random copolymer condensate. As for the base polymer of the positive photosensitive resin composition of the present invention, the above-mentioned base polyamine can be copolymerized with the polyanilin unit, and the copolymerization ratio in the copolymerization can be Optionally, from the viewpoint of photosensitivity, it is preferred that the polybenzo W precursor unit: the ratio of the polyimine unit is ι〇: 90-100: range of 〇. (A) Soluble polymerization of an aqueous alkaline solution Preferably, the end of the substance is selected from the end of the table * represented by the following formula (6) Shu group consisting of at least a kind of terminal groups. [Formula 20]

(6)

U {wherein' L5 represents a group selected from the group consisting of ·CIi2...〇_ and each of the groups, and u represents a hydrogen atom or an alkyl group}. Not only the above formula (6) but also the terminal group described below can be used for the modification. As a modification of the end, (4) soluble (four) lipid synthesis, add appropriate amount of shun shun (four) liver, cinnamon, 5 (four) acid liver, 4 ethynyl phthalate liver, phenyl ethynyl benzene Dicarboxylic acid needle, 3,6-epoxy-^^, hydrogen phthalic acid ^heart ring-diluted - 140356.doc •25· 201011465 1,2-diphthalic anhydride, cyclohexene-1,2-two曱 轩 、, 4-methylcyclohexan-2-one acid liver, 4-aminophenethyl benzoate, 4-ethylhexyl aniline, &gt; eimetanilide, 4-aminophenol, 3-aminophenol , 2-amino phenol or the like can be used. Further, the dicarboxylic acid used in the present invention may be left as a terminal. (A) polystyrene of gel permeation chromatography (hereinafter also referred to as r Gpc) of an aqueous solution of a water-soluble solution; the weight average molecular weight of ethylene is preferably 3, 〇〇〇~5 Oh, better is 6'000~30,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of physical properties of the hardened relief pattern. Further, from the viewpoint of analyticity, it is preferably 5 M00 or less. As a developing solvent for GPC, tetrahydrofuran (hereinafter also referred to as "THF") and N-methyl-2_pyrr〇Ud〇ne (hereinafter also referred to as NMP) are recommended. Further, the molecular weight was determined based on a calibration curve prepared using standard monodisperse polystyrene. As a standard monodisperse polystyrene, it is recommended to be selected from the standard solvent STANDARD SM-105 manufactured by Sigma and Electrician A. (B) Photoacid generator 睡 Sleeping: W photoacid generator 'can use a naphthalene-doped azide compound, 镔-3 has a compound of i, etc.' but in terms of solvent solubility and storage stability, A compound having a naphthene diazide structure (hereinafter also referred to as "naphthoquinonediazide compound") is preferred. The above-mentioned onium salt may, for example, be a salt of a town or a salt of a sulfonium salt, and is preferably an onium salt selected from the group consisting of a phosphonium salt of a diarylsulfonium salt. Anthracene salt, ammonium salt, diazotriaryl salt and eucommia; 140356.doc -26· 201011465 As the above-mentioned compound containing _, there is a hydrocarbon compound containing a halogen-based compound, preferably trichloroantimony Plowing. The naphthoquinonediazide compound is a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure, according to the specification of U.S. Patent No. 2,772,972, and the specification of U.S. Patent No. 2,797,213. A material well known in the specification of U.S. Patent No. 3,669,658. The naphthoquinonediazide structure is selected from the group consisting of 1,2-naphthoquinonediazide-4-sulfonate having a specific structure of a polyhydroxy compound as described below, and 1,2-naphthalene of the polyhydroxy compound. At least one compound of the group consisting of quinonediazide-5-sulfonate (hereinafter also referred to as "NQD compound"). The NQD compound can be obtained by using a sulfinic acid or a sulfinium chloride to form a naphthoquinonediazidesulfonic acid compound into a sulfonium chloride to obtain a naphthoquinonediazide sulfonium chloride and a polyhydroxy compound. It is obtained by carrying out a condensation reaction. For example, by using a poly-based compound with a specific amount of 1,2-naphthalene, a mixture of -5 - chlorobenzene or 1,2-naphthalene S-quinonediazide-4-anthracene chloride, on the 11th In a solvent such as calcination, acetone or tetrahydroanthracene, it is reacted in the presence of an alkaline catalyst such as triethylamine to carry out esterification, and the obtained product is washed with water and dried. The preferred NQD compounds are disclosed below. An NQD compound of a polyhydroxy compound represented by the following formula (10) [Chem. 21]

140356.doc -27- 201011465 In the case of ~n5, respectively, 1 or 2'r]~Rio are independent of free hydrogen atoms, dentate stands for phenanthrene, and at least 1 of propyl group The monovalent group, Y4~Υ6, respectively, is selected from the group consisting of a single bond, η 0 〜 independent of the bond -〇-, -SO-, -so2-, _C〇·, _Γη cyclopentyl, arylene, 4 丄U2-, a subtle base, and at least one divalent group consisting of a group consisting of the following chemical formulas}

Wherein Rn&amp;Rn independently represents at least one selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an allyl group, and a substituted allyl group.

In the formula, Rn-Rw represents a hydrogen atom or an alkyl group, respectively, which may be the same or different, and m3 represents an integer of 1 to 5} [Chem. 24]

In the formula, R 7 to R2 〇 indicates that the SL atom or the alkyl group may be the same or different. 140356.doc • 28 - 201011465 As a specific compound, there is an NQD compound of a polyhydroxy compound disclosed in [Chem. 18] to [Chem. 32] of JP-A-2001-109149. Among them, the NQD compound of the following polyhydroxy compound is preferred because of its high sensitivity and low precipitation in the positive photosensitive resin composition. [Chem. 25]

NQD compound of a polyhydroxy compound represented by the following formula (11) [Chem. 26]

(Π) wherein x6 represents at least one tetravalent group selected from the organic group represented by the following chemical formula, R21 to R24 each independently represent a monovalent organic group, 1 represents 0 or 1, and m4 to m7 are each independently An integer representing 0 to 3, and n6 to n9 each independently represent an integer of 0 to 2} 140356.doc -29- 201011465

As a specific compound, it is disclosed in [Chem. 23] to [Chem. 28] of JP-A No. 2〇01·〇92138, which is preferable because of high sensitivity and low properties. . Among them, the precipitation of the following polyhydroxy compound in the positive photosensitive resin composition

[化 28]

140356.doc -30- 201011465 [Chem. 30]

[化31]

NQD compound of a polyhydroxy compound represented by the following formula (12) [Chem. 32]

In the formula, m8 represents an integer of 3 to 8, and m8xj L14 independently represent a monovalent organic group having 1 140356.doc -31 - 201011465 or more carbon atoms 'j represents an integer of u, called machine 12, and called L, 3 independently represent a hydrogen atom or are selected from! The monovalent group in the group consisting of valence organic groups}. A preferred example of the invention is disclosed in [Chem. 24] and [Chem. 25] of the Japanese Patent Publication No. 3479〇2. Among them, the NQD compound of the following polyhydroxy compound has high sensitivity and is preferably low in the positive photosensitive resin composition. [化33]

{where, p is an integer from 0 to 9}. An nqd compound of a polyhydroxy compound represented by the following formula (13)

In the formula, M2 represents an aliphatic divalent organic group having a tertiary or quaternary carbon, and octa 3 represents at least one divalent group selected from the group represented by the following chemical formula: 140356.doc -32- 201011465 [Chem. 35] CH3 cf3 o ch3 CFi o II -c- 2003-131368 The specific compound is disclosed in Japanese Patent No. [22] to [Chem. 28]. The NQD compound of the poly-based compound under the eight-phase X has high sensitivity due to its high sensitivity.

The positive photosensitive resin composition has a low precipitation property and is preferred. [化36]

Wherein L represents 5 a group selected from the group consisting of _CH2..._〇_ and _8•, and Li6 represents a hydrogen atom or an alkyl group] -33· 140356.doc 201011465 [Chem. 38]

In the formula, L丨7 represents a group selected from the group consisting of _CH2-, -〇-, and -S-, and L18 represents a hydrogen atom or an alkyl group] a polyhydroxy group represented by the following formula (14) NQD compound of compound [39]

The one-valent organic group is shown as an integer of 0 to 2} The cloth is not the same as the other, and the same is true, and m9~m] [化40] (^28&gt;〇1|2

140356.doc -34- 201011465 {wherein r28 is independently represented by a hydrogen atom, at least one monovalent organic group selected from the group consisting of an alkyl group and a cycloalkyl group, and mi2 is independently an integer of 〇~2}. The specific compound is an NQD compound of a polyhydroxy compound disclosed in [Chem. 17] to [Chem. 22] of JP-A-2004-109849. The NQD compound of the following polyhydroxy compound is preferred because of its high sensitivity and low precipitation in the positive photosensitive resin composition. [化41]

140356.doc -35- 201011465 [Chem. 43]

The NQD compound of the polyhydroxy compound shown is represented by the following formula (ls) [Chem. 44]

In the formula, R29 represents a hydrogen atom and at least one monovalent organic group selected from the group consisting of an alkyl group, an alkoxy group and a ring-based group. D is an organic compound and is not disclosed in [Chem. 18] to [Chem. 22] of JP-A-2001-356475. The NQD compound of the following polyhydroxy compound is preferred because of its high sensitivity and low precipitation in the positive photosensitive resin composition. 140356.doc •36· 201011465 [Chem. 45]

NQD compound of a polyhydroxy compound represented by the following formula (16) [Chem. 46]

The same or different, ~_ each independently represents an integer of 〇~2, and ~Han is not selected from a hydrogen atom. One of the alkyl or cycloalkyl groups. [Chem. 47] (R34) mt6

Wherein r34 each independently represents a hydrogen atom, is selected from an alkyl group and a cycloalkyl group, and is at least one monovalent organic group, and 6 is an integer of 〇~2. As a specific compound, the original system is not disclosed in the Japanese Patent Laid-Open Publication No. 2005_008626, pp. 151, (Άία丄

The N compound of the polyhydroxy compound in L Ν [Chemical Formula 16]. In the above, the NQD compound of the polyhydroxy compound is preferably high in sensitivity and low in precipitation in the positive photosensitive resin composition. [化48]

As another structure, specifically, the following structure is preferable. 140356.doc -38 - 201011465 [Chem. 50]

In the present composition, the naphthoquinonediazidesulfonyl group in the NQD compound is preferably any one of a 5-naphthoquinonediazidesulfonyl group and a 4-naphthoquinonediazidesulfonyl group. . The 4-naphthoquinonediazidesulfonyl ester compound has absorption in the i-line region of the mercury lamp, and is therefore suitable for i-line exposure. The absorption of the 5-naphthoquinonediazidesulfonyl ester compound extends to the g-line region of the mercury lamp, and is therefore suitable for g-line exposure. In the present invention, it is preferred to select a 4-naphthoquinonediazidesulfonyl ester compound or a 5-naphthoquinonediazidesulfonyl ester compound depending on the wavelength of exposure. Further, a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group may be used in the same molecule, or 4-naphthalene may also be used. The quinonediazidesulfonyl ester compound is used in combination with a 5-naphthoquinone diazide. In the present composition, the amount of the naphthoquinonediazide compound to the alkaline aqueous solution-soluble polymer is 1 to 50 parts by mass, preferably 5 to 5 parts by mass based on 100 parts by mass of the alkaline aqueous solution-soluble polymer. 30 parts by mass. When the amount of the photosensitive diazonium compound is 1 part by mass or more, the patterning property of the resin is good. On the other hand, if it is 50 parts by mass or less, the film has a good tensile elongation after curing and is exposed. Developing residue (sponge), less than 140356.doc -39- 201011465 As (c) a compound represented by the following general formula (2), a bisallyl nadic ylidene compound or a double hydrazine can be cited. An enelimine compound or the like. From the viewpoint of sensitivity, it is more preferable to contain a compound of the following formula (3). Specific examples of the compounds are exemplified by the general formula (3) (manufactured by Maruzen Petrochemical Co., Ltd.: trade names BANI-M, BANI-X, BANI-H, BANI-D). Among the compounds of the formula (3), BANI-X is preferred from the viewpoint of curing shape and sensitivity. [化 51]

Wherein 'Di has at least one functional group selected from the group consisting of a hydrogen atom, a carbon number of a carbon number 6, an alkenyl group, and a crosslinkable organic group, and the river 1 is selected from the group consisting of -CH2·, -〇 · and -S- group of groups, 21 is a divalent organic group, (1) is an integer of 0 to 4' and when there are a plurality of 0丨, a plurality of 〇1 may be the same or different&gt; 140356.doc •40- 201011465

[化52]

Αανι-η

(3) The compound (c) may be used singly or in combination of two or more. The compounding amount of the (c) compound is from 1 to 40 parts by mass, more preferably from 2 to 3 parts by mass, even more preferably from 4 to 20 parts by mass, per 100 parts by mass of the (aqueous) aqueous solution of the soluble polymer. . When the compounding amount of the compound is at least a part by mass, the cured shape at the time of curing is good. On the other hand, if it is 4 parts by mass or less, the film has a good tensile elongation after curing and exhibits a good 140356. Doc - 41 - 201011465 Adhesion and lithography performance. (D) Organic solvent In the present invention, it is preferred that the components are dissolved in a solvent to form a varnish, and thus used as a photosensitive resin composition solution. As such a solvent, the following solvents may be used singly or in combination: N-methyl-2-pyrrolidine

嗣, γ-butyrolactone (hereinafter also referred to as "GBL"), cyclopentate, cyclohexanide, isophorol, and N,N-dimethyletheneamine (hereinafter also referred to as "DMAc"), Dimethyl meraldone, methyl gland, dimethyl sub-, diethylene glycol dimethyl bond (hereinafter also referred to as "DMDG"), diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol Monochamus, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate vinegar, lactic acid f vinegar, lactic acid acetate, lactic acid butyl vinegar, 1,3-butanediol methyl acetate, hydrazine, 3 - butanediol _3_monomethyl ether, methyl acetonate, ethyl acetoacetate, methyl 3-methoxypropionate, and the like. Among these solvents, a non-melamine-based solvent is preferred because it has little effect on the photoresist or the like. As a more specific example, γ·butyrolactone, lactic acid brewing, propanol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, tetrahydrogen can be mentioned.

Sterols and the like. These organic solvents may be used singly or in combination of two or more. Compared with 100 parts by mass of the (aqueous) aqueous solution of the alkaline aqueous solution, the amount of the (D) solvent is adjusted to be 1 〇〇 2 2 parts by mass and the viscosity can be controlled by changing the amount of the organic solvent added. . It is preferably 1 〇〇 to 1 〇〇〇 mass damage, more preferably 1 〇〇 to 1 〇〇〇 parts by mass, and when the amount of the solvent added is within the above range, it is set to be suitable for the coating device and coating. The viscosity of the cloth thickness makes it easy to manufacture the hardened relief pattern, which is preferable. 140356.doc -42· 201011465 (E) Other additive-based tree gambling compositions, if necessary, may be added as a positive-type photosensitive resin combination: as an additive, and may be added as a positive photosensitive resin combination: A compound, a dye, a surfactant, at least one of a bonding aid for improving adhesion to a germanium wafer, and the like. Further, the additive is more specifically described, and the compound having a transbasic group preferably has a carbon number of 4 to 14. From the viewpoint of sensitivity and resolution, it is preferable to add a compound containing a hydroxyl group to the photosensitive resin composition of the present invention. Bamboo ^•人+ ^ As a compound having 3 hydroxyl groups, specific examples thereof include cyclopropanol, 2_cyclohexene]-alcohol, cyclohexane methanol, and 4-methyl-1-cyclohexanemethyl 1 3 '4-Methylcyclohexanol, 4-ethylcyclohexanol, 4_t-butylcyclohexanol, cyclohexaneethanol, 3·cyclohexylmalpropanol, Cyclohexyl”·pentanol, , 5 —nonylcyclohexanol, normoxime-2-methanol, cyclonic acid, 2,3,4-trimethyl-3-pentanol, 24- Ρ-α, hexen-1-ol, Cis_2_hexene-1-alcohol, trans-2-heptene-enzyme, cis-4-heptane+alcohol, cis-3-octene diol, 4_ethyl octyl acetylene Monoenol, 3,6'didecyl-1-heptyn-3-ol '3-ethyl-2-methyl-3-pentanol, 2-r 1 ai ethyl-1-hexanol, 2,3-Dimethyl-2-hexanol, 2,5-dimethylhexanol, and) _9 &amp; τ , , 壬 稀 dilute alcohol, 1- 壬 dil-3-ol, cis_2_ Ding Fu-1,4-diol '2 7 · Gan _ , ethyl -1,3-propanediol, 2,4-diethyl _1,5-pentanol hexamethylene _3,4' diol 2,5-Dimethyl-3-hexyne-2,5-diol 2'4'7,9-tetramethyl-5~decyne-4,7-diol, 2,2,4, 4-tetramethyl_13_cyclobutanediol, 丨2_cyclop Alcohol, trans-p-menthane-3,8-diol, 2 4-indolyloxybenzyl alcohol, butyric acid, etc. One 140356.doc -43- 201011465 Among these, 'better is 2,3 , Rensan Lane·~3-sterol, 24-P-, 咕1-alcohol, cis-hexenol, anti-cardiac _, hexene-ene nectar-1-ol, cis_4_g Alcohol, cis-3-octene-indole-alcohol, anti-cis, 2,6_壬_ olefin-1-enzyme, α-di-dipeptide-containing compound containing m-group, and The branching early alcohol is superior to the second fermentation. Among them, 'excellent is 2,3,4_trimethyl 3-ethyl-2-methyl-3-pentanol, glycerol·丨-土0-qing propyl shout. These hydroxyl group-containing compounds may be used singly or in combination of two or more kinds. The compounding amount of the above-mentioned compound containing a mercapto group may be blended with respect to the (10) parts by mass of the water-soluble polymer of the test aqueous solution. Preferably, 〇~7〇 parts by mass, more preferably (Μ~50 parts by mass) is particularly preferably Η〇 by mass, especially preferably 5 to 25 parts by mass. If the compound having a hydroxyl group is 0.01 If the mass is more than the above, the development residue of the exposed portion is reduced. On the other hand, if it is 70 mass In the following, the stretched elongation of the film after curing is good. Examples of the phenol compound include a ballast agent used in the above-mentioned photosensitive diazonium compound, p-nonylphenol, bisphenols, and isophthalic acid. A linear phenolic compound such as a phenolic compound such as MtrisPC or MtetraPC (manufactured by Honshu Chemical Industry Co., Ltd.: trade name), a non-linear phenolic compound such as TrisP-HAP, TrisP-PHBA, and TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.: trade name A compound in which 2 to 5 hydrogen atoms of a phenyl group of diphenylmethane are substituted with a hydroxyl group, a compound in which a hydrogen atom of a phenyl group of 2,2-diphenylpropane is substituted with a hydroxyl group, or the like. By adding the phenol compound, the adhesion of the convex pattern at the time of development can be improved, and the occurrence of the convex pattern can be suppressed. Further, the pulverized compound of the "four-membered hydrogen atom" is a phenol compound which is used as a raw material in the above-mentioned photosensitive diazonium compound. The amount of the aqueous solution-soluble polymer is 100 parts by mass, and the amount of the compound is preferably 0 to 50 parts by mass, more preferably 1 to 30 parts by mass. When the amount added is within 5 parts by mass, the heat resistance of the film after heat curing is good.

W As a dye, a methyl violet, a crystal violet, a malachite green, etc. are mentioned, for example. The blending amount in the case of formulating the dye is preferably O.hW parts by mass based on 100 parts by mass of the alkaline aqueous solution-soluble polymer. When the amount of addition is 1 〇 by mass or less, the heat resistance of the film after heat curing is good. Examples of the surfactant include nonionic surfactants including polyglycols such as polypropylene glycol or polyoxyethylene lauryl ether and derivatives thereof. Further, a fluorine-based surfactant such as Fluorad (manufactured by Sumitomo 3M Co., Ltd.), Megafac (manufactured by Daiichi #Ink Chemical Industry Co., Ltd.: trade name), or Lumiflon (manufactured by Asahi Glass Co., Ltd.) is used. Further, an organic stone oxy-oxygenated surfactant such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name), DBE (manufactured by Chisso Co., Ltd.), and Glan〇l (manufactured by Kyoeisha Chemical Co., Ltd.) can be cited. By adding the surfactant, shrinkage of the coating film at the edge of the wafer at the time of coating can be made more difficult. The blending amount in the case of formulating the surfactant is preferably from 〇1 to 1 part by mass, more preferably from 0.01 to 1 part by mass, based on 1 part by mass of the water-soluble polymer of the aqueous solution. If the amount added is within 1 part by mass, the heat resistance of the film of 140356.doc -45 - 201011465 after heat hardening is good. Examples of the subsequent auxiliary agent include various decane coupling agents such as alkyl imidazolium, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, third butyl phenol aldehyde, epoxy polymer, and epoxy decane. . Specific examples of the ceramsite coupling agent include 3-carbopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM8〇3, manufactured by Chisso Co., Ltd.: trade name Sila_Ace S810 ), 3-sodium propyl triethoxy sulphur (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropyl decyl decyloxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: Trade name: LS1375, manufactured by Azmax Co., Ltd.: trade name SIM6474 〇), mercapto decyl trimethoxy decane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethyl decyl decyloxy decane (Azmax shares) Manufactured by: Ltd.: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxydecane, 3-mercaptopropylethoxydimethoxydecane, 3-mercaptopropyldipropoxydecane , 3-mercaptopropyldiethoxypropoxydecane, 3-sulfopropylethoxydipropoxydecane, 3-mercaptopropyldimethoxypropynyldecane, 3-mercaptopropylmethyl Oxydipropoxydecane, 2-decylethyltrimethoxydecane, 2_巯Benzyldiethoxymethoxydecane, 2-mercaptoethylethoxydimethoxydecane, 2-mercaptoethyltripropoxydecane, 2-mercaptoethyltripropoxydecane, 2 Mercaptoethylethoxy-propoxydecane, 2-mercaptoethyldimethoxypropoxydecane, 2-mercaptoethylmethoxydipropoxydecane, 4-decylbutyltrimethoxydecane, Mercaptobutyl diethoxy decane, 4_mercaptobutyl tripropoxy hydrazine 140356.doc • 46· 201011465 Alkane, N-(3-triethoxydecylpropyl)urea (Shin-Etsu Chemical Industry Co., Ltd. Manufactured by trade name: LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0), N-(3-trimethoxyoxyalkylalkyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N- (3-diethoxymethoxydecylpropyl)urea, N-(3-ethoxydidecyloxydecylpropyl)urea, N-(3-tripropoxydecylpropyl) Urea, N-(3-diethoxypropoxydecylpropyl)urea, N-(3-ethoxydipropoxydecylpropyl)urea, N-(3-dimethoxypropane) Oxidylalkylpropyl)urea, N-(3-methoxydipropoxy) Alkylpropyl)urea, anthracene-(3·trisethoxydecylethyl)urea, anthracene-(3-ethoxydidecyloxydecylethyl)urea, anthracene-(3-tripropoxyl) Alkylethyl)urea, Ν-(3-tripropoxydecylethyl)urea, Ν-(3-ethoxydipropoxydecylethyl)urea, Ν-(3-dioxin Oxypropoxyalkylalkylethyl urea, Ν-(3-methoxydipropoxydecylethyl)urea, Ν-(3-trimethoxydecylbutyl)urea, hydrazine-(3 -triethoxydecyl butyl)urea, hydrazine-(3-tripropoxydecyl butyl)urea, 3-(m-aminophenoxy)propyltrimethoxy decane (Azmax Corporation) Manufactured: trade name: SLA0598.0), m-aminophenyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name: SLA0599.0), p-aminophenyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SLA 〇599.1), aminophenyl trimethoxy decane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(trimethoxy sulphate ethyl) mouth bite (manufactured by Azmax Co., Ltd.: Product name SIT83 96.0), 2-(triethoxydecylethyl Pyridine, 2-(dimethoxydecylalkyl decylethyl)pyridine, 2-(diethoxydecylmethylethyl)pyridine, (3-triethoxydecylpropyl)amine 140356.doc • 47- 201011465 tert-butyl carboxylic acid, (3-glycidoxypropyl) triethoxy decane, and the like. Moreover, as a particularly preferable decane coupling agent, the following structures are mentioned, but it is not limited to this. [化53]

Ο丄Η- (CH2)3-Si(OC2H5)3 Ο

aC-NH-(CH2)j-SK〇C2H5)3 COOH is preferably 〇20-20 parts by mass, based on 100 parts by mass of the alkaline aqueous solution-soluble polymer, in the case of formulating the above-mentioned secondary auxiliary agent. It is preferably 0.05 to 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, particularly preferably 1 to 6 parts by mass. When the amount of the oxime coupling agent is not more than 1 part by mass, the exposed portion has no development residue, and the adhesion to the ruthenium substrate is good. On the other hand, if it is 20 parts by mass or less, the adhesion is good. Good aging stability. Further, the following compounds can be used in combination. Specific examples thereof include tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetraisopropoxy decane, tetra-n-butoxy decane, tetraisobutoxy decane, and tetra-butoxy group. Decane, tetrakis(decyloxyethoxydecane), tetrakis(decyloxyn-decyloxydecane), tetrakis(ethoxyethoxydecane), tetrakis(methoxyethoxyethoxydecane), Bis(trimethoxydecyl)ethane, bis(trimethoxydecyl)hexane, bis(triethoxydecyl)decane, bis(triethoxydecyl)ethane, bis (triethyl) Oxygen 140356.doc •48- 201011465

Base alkyl) ethylene, bis(triethoxydecyl)octane, bis(triethoxyxanthene)octadiene, bis[3-(triethoxydecyl)propyl]disulfide , bis[3_(diethoxyxanthyl)propyl]tetrasulfide, di-t-butoxydiethyloxylate, diisobutoxyaluminoxytriethoxydecane, double Acetylacetone) titanium-ruthenium, osmium, -bis(oxyethyl)-aminopropyltriethoxydecane, and the like. Among them, tetramethoxy decane and tetraethoxy decane are particularly preferable. The compounding amount of the above compound relative to the alkaline aqueous solution soluble polymer is preferably 〇〇 parts by mass, more preferably 0·b 6 parts by mass, particularly preferably 100 parts by mass of the alkaline aqueous solution-soluble polymer. Bu 4 parts by mass. When it is 1 part by mass or more, the exposure portion has no development residue, and the adhesion to the ruthenium substrate is good. In addition, when it is 10 parts by mass or less, the aging-resistant photosensitive resin composition is adhered. In addition to the above compound (c), a crosslinking agent may be added. As a crosslinking agent, it is possible to use (4) to crosslink the anti-red compound with heat and the soluble tree. Here, the temperature of the reaction of the riding (4) is preferably (9) to 3501. The crosslinking reaction occurs when the heat treatment is carried out by development _. The chemical resistance or the substance is improved. Preferably, the following compound is added.孜 140356.doc •49· 201011465 [Chem. 54]

HjCOH2C pH

CHjOCHj

HiCX&gt;H2C

140356.doc •50 201011465 [Chem. 55]

H1COH2^n^n^.CH1OCHj

HjC0H2C, HaCOHjC H)COH2C-KH-C-KH-CH2OCHj

HjCHjCOHjC-NH-C-NH-CHiOCHiCHj

HjCOHj^ ^CtfcOCHj H2CV J^NJkN^cK2〇CHj CHjO OCHj h~{

HjCH2CO OCK2CH)

H

HjCHiCOHjC Y ^CHjOCHjCHj In addition to the above crosslinking agent, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, cresol novolac type epoxy resin, phenol novolak type ring Oxygen resin, glycidylamine type epoxy resin, polysulfide type epoxy resin, MX270 (manufactured by Sanwa Chemical Co., Ltd.), MX; 280 (manufactured by Sanwa Chemical Co., Ltd.), dimethyl urea, trimethyl melamine, six Hydroxymercapto melamine, dimethylol ethylene urea, dihydroxyl 51 - 140356.doc 201011465 base = dilute gland, I4-bis(decyloxyphenoxy)benzene, trimethoxymethyl tri A*amine, A Oxymethylmethyl melamine, diethylene glycol diallyl ether, two strains of oxypic acid &amp; propyl sulfonate, diallyl hexahydrophthalate, and the like. Among these, from the viewpoint of preserving stability, a compound having a base of alkoxy bauxite, wherein the base polymer used for the photosensitive resin composition is formed into a cyclized resin, is preferred. In terms of the effect of the time-dependent deformation reduction, 5' is preferably a compound having an alkoxymethyl group. As for the case where the crosslinking agent component is blended, the pattern is opened in the heat of development, and the allowable range of the residue generated during development is δ, relative to the alkaline aqueous solution soluble polymer 1〇. The mass part is preferably 0.5 to 5 parts by mass, more preferably 5 to 2 parts by mass. &lt;Cured embossed pattern, and method of manufacturing semiconductor device&gt; Next, a method of manufacturing the cured embossed pattern of the present invention will be specifically described below. (1) A step of forming a photosensitive resin layer containing a photosensitive resin composition on a substrate (first step). The photosensitive resin composition solution is applied to a substrate such as a ruthenium, a ceramic substrate, or an aluminum substrate by spin coating using a spin coater or a coater such as a die coater or a roll coater. on. The oven or the hot plate is used to apply heat of 50 to 140 ° C, preferably 100 to 140 °, and to remove the solvent (hereinafter also referred to as "soft roast" or "pre-bake"). (2) A step of exposing or directly illuminating the 'electron beam or ion beam' with actinic rays via a reticle (second step). Then, the photosensitive resin layer is exposed to actinic rays through a photomask using a contact aligner or a stepper, or directly irradiated with light, an electron beam or an ion beam. As the active light, a g-line, an h-line, an i-line, or a Μ laser can also be used. (3) a step of eluting or removing the exposed portion or the irradiated portion (third step, followed by dissolving the developing solution to remove the exposed portion or the irradiated portion, followed by elution with the eluent) to thereby obtain a desired embossed pattern As the developing method, distilled water, deionized water, or the like can be used by means of spraying, stirring, dipping, ultrasonication, etc. The eluent can be used.

The developer for developing the film formed of the photosensitive resin composition is a test solution in which the soluble polymer is dissolved and removed, and it is necessary to dissolve the test compound. The test compound dissolved in the developer may be either an inorganic compound or an organic test compound. Examples of the inorganic basic compound include, for example, lithium hydroxide, sodium hydroxide, hydrogen hydroxide, hydrogen hydrogen dihydrogen phosphate, phosphoric acid di-nano, ton, 11 money, potassium, rhyme, carbonic acid. Potassium, lithium borate, sodium borate, potassium borate and ammonia. Further, as the organic test compound, for example, tetramethyl oxyhydrin, tetraethyl hydroxyoxyl, trimethyl hydroxyethyl hydroxyacetate, methylamine, dimethylamine, trimethylamine, and monoethyl bromide may be mentioned. Amine, diethylamine, triethylamine, n-propylamine 'di-n-propylamine, isopropylamine, diisopropylamine, methyldiethylamine, dimethylethanolamine, ethanolamine and triethanolamine. Further, if necessary, an appropriate amount of a water-soluble organic solvent such as methanol, ethanol tripropanol or ethylene glycolate may be added to the aqueous solution, and a surfactant, a stabilizer, and a dissolution inhibitor of the resin may be stored. 140356.doc -53- 201011465 (4) Step of heat-treating the obtained embossed pattern (fourth step) Finally, the obtained embossed pattern is subjected to heat treatment (hereinafter this step is referred to as "cure"), thereby forming an inclusion A heat-resistant hardened relief pattern of a resin having a polybenzoxazole structure. As the heating means, an oven furnace, a 9-heating plate, a vertical furnace, a conveyor belt furnace, a pressure oven, or the like can be used, and as a heating method, heating by hot air, infrared rays, electromagnetic induction or the like is recommended. The temperature is preferably 200 to 450 ° C, more preferably 250 to 400 t ^, and the heating time is preferably 15 minutes to 8 hours, more preferably i hours to 4 hours. Further, it is preferable that the ambient gas is in an inert gas such as nitrogen or argon. The semiconductor device produced by using the photosensitive resin composition of the present invention can be used as a surface protective film, an interlayer insulating film, an insulating film for rewiring, or a flip chip device by using a cured embossed pattern containing the photosensitive resin composition. A protective film of a protective film or a device having a bump structure is produced in combination with a manufacturing method of a known semiconductor device. Further, the photosensitive resin composition of the present invention can be effectively used for the interlayer insulating film of a multilayer circuit, the protective ruthenium of a flexible copper foil plate, a solder resist film, a liquid crystal alignment film, or the like. [Examples] Hereinafter, the present invention will be described by way of Reference Examples and Examples. [Reference Example 1] &lt;Production of bis(carboxyl)tricyclo[5,2,1,02'6]decane>To glass to which an anchor type stirrer made of Teflon (registered trademark) was attached In a separable three-necked flask, 71.9 g (〇366 m〇1) of tricyclo[5,2,1,02'6]indole dimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in i [140356. Doc -54· 201011465

The solution obtained in the acetonitrile was added thereto to dissolve 256.7 g (l.808 mol) of monosodium hydrogen phosphate and 217.1 g (1.808 mol) of sodium dihydrogen phosphate in 1 4 L of ion-exchanged water. Solution. To this, 28 g (〇〇179 mol) of 2,2,6,6-tetradecylpiperidinyloxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter also referred to as "TEMPO") was added and stirred. Let it dissolve. 143.2 g (l.267 mol) of 80% sodium chlorite was diluted with 850 mL of ion exchange water and added dropwise to the above reaction solution. Then, 37 mLi of φ 5% sodium hypochlorite aqueous solution was diluted with 7 mL of ion-exchanged water, and added dropwise to the reaction liquid. The reaction solution was maintained at 35 to 38 &lt; t using a thermostatic chamber, and allowed to react for 20 hours.

After the reaction, the reaction solution was cooled to 12 ° C, and an aqueous solution obtained by dissolving 75 g of sodium sulfite in 300 mL of ion-exchanged water was added dropwise to the reaction solution to deactivate the excess sodium chlorite, and then use 5 Torr. 〇mL of ethyl acetate was washed. Thereafter, 115 mL of 1% hydrochloric acid was added dropwise to the reaction solution? The value of 11 was adjusted to 3 to 4, and the precipitate was recovered by decantation. The precipitate was dissolved in 200 mL of tetrahydrofuran. Further, the aqueous layer was extracted twice with 500 mL of ethyl acetate, and then washed with brine to dissolve the precipitate in a tetrahydrofuran solution. The above tetrahydrofuran solution was mixed and dried over anhydrous sodium sulfate. The solution was concentrated and dried by an evaporator to obtain a white crystal of bis(carboxy)tricyclo[^, (yield: 71.1%). [Reference Example 2] <Manufacture of bis(gas rebel) tricyclo[5,2,1,02'6]decane&gt; 62.5 g (278 mmol) of the bis(carboxyl group) obtained in Reference Example 1 Tricyclic 140356.doc -55- 201011465 [5,2,1,02'6] decane, 97 111 [(1.33 11191) of sulfite chlorine and 〇41111^5() mmol) The reaction vessel was stirred at 25 to 50 ° C for 18 hours to react. After the completion of the reaction, 'toluene was added, and excess sulfite gas was azeotroped with toluene under reduced pressure to concentrate, thereby obtaining 73.3 g (100% yield) of oily bis(gas carbonyl) tricyclo[5 , 2, 1, 02, 6] decane. [Reference Example 3] &lt;Synthesis of aqueous solution of detectable aqueous solution&gt; In a separable flask having a capacity of 2 L, 197.8 g (〇.54 mol) of 2,2-bis(3-amino group- 4-Phenylphenyl)hexafluoropropane, 75.9 g (〇·96 mol) of &quot;bipyridine and 692 g of DMAc were mixed at room temperature (25 ° C) to dissolve the same. Further, 19.7 g (〇.12 m()1&gt; of 5-norkenylene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 8 g of DMDG by using a dropping funnel. The time required for the addition is 4 〇 minutes, and the temperature of the reaction liquid is at most 28 ° C. After the end of the dropwise addition, the temperature is raised to 5 by a hot water bath (TC and stirred for 8 hours, then the reaction solution The IR spectrum (infrared light error) was measured, and it was confirmed that the characteristic absorption of the quinone imine group was exhibited at 1385 cm-1 &amp; 1772 cm_i. Then, it was cooled to 8 by a water bath. Separately, 142.3 g (0.48 mol) of 4,4,-diphenyl ether dimethyl hydrazine gas was dissolved in 398 g of 2DMDG by using a dropping funnel. The time required for the dropwise addition was rib minutes, and the temperature of the reaction liquid was The maximum is 12〇C. After 3 hours from the end of the dropwise addition, the above reaction solution is added dropwise to 12 L of water under high-speed stirring to disperse and precipitate the polymer 'recover it' in a suitable water washing, dehydration and vacuum drying. 140356.doc -56- 201011465 Alkali-soluble resin (pi). Alkali soluble in the above manner The weight average molecular weight (Mw) measured by GPC (gel permeation chromatography), a single steep λ sharp curve converted to 14,000 in terms of polystyrene, a single composition. Analysis of GPC The conditions are as follows: Column: manufactured by Showa Denko, trade name Shodex 805/804/803 tandem eluent: tetrahydrofuran, 40 ° C Flow rate: 1.0 ml / min

Detector: manufactured by Showa Denko, trade name Shodex RI SE-61 [Reference Example 4] To a glass separable two-necked flask equipped with a Teflon (registered trademark) anchor type agitator, 69.17 g (268) was added. Methyl) bis (3-amino _4_ basic) propylene (manufactured by Clariant Japan) (hereinafter also referred to as BAP), 276 g of NMP and 12.7 g (160 mmol) of bite, then A nitrogen gas introduction tube was attached to the flask, and the mixture was stirred under a nitrogen gas flow to dissolve the hydrazine. After the solution was dissolved, the reaction vessel was immersed in a vessel in which dry ice was added to methanol for cooling. 69 99 mmol) of the bis(gas carbonyl)tricyclo[5,2a , 〇 2,6] decane produced in Reference Example 2 was dissolved in 280 § 1/-butyrolactone and kept at _1 〇 ~_19. (: and added dropwise to the reaction vessel over a period of 3 minutes. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 0 to 10 «c and stirred for 2 hours. Further, eight 29.65 g (375 mmol) Oral ratio 唆0 To the above reaction solution, ethanol was added to precipitate the polymer, which was then recovered and dissolved in 350 mL of NMP. Then, 78 g of cationic oxime resin (Amberlyst A21, manufactured by Organo Co., Ltd.), 75 g was used. Negative = change 140356.doc •57- 201011465 Replacing resin (Amberlyst 15 manufactured by Organo, Inc.) for ion exchange. The solution was added dropwise to 3 L of ion-exchanged water under high-speed stirring to disperse and precipitate the polymer. After appropriate washing with water and dehydration, vacuum drying is carried out to obtain an alkali-soluble resin (P-2) containing a PBO precursor unit. The weight average molecular weight measured by GPC of the alkali-soluble resin synthesized in the above manner is converted into polystyrene. A single steep curve of 36800 is a single composition. The analysis conditions of GPC are as follows. Column: manufactured by Showa Denko, trade name Shodex 805M/806M

Eluent: N-decylpyrrolidone, 40 ° C Flow rate: 1.0 ml / min Detector: manufactured by JASCO Corporation, trade name RI-930 [Reference Example 5] Mounted with Teflon (registered trademark) In a glass separable three-necked flask of anchor stirrer, 91.56 g (250 mmol) of 6FAP, 183 g of DMAc, 550 g of GBL, and 25 g (315 mmoUinit11) were dissolved to dissolve 6FAP. After 6FAP was dissolved, The reaction vessel was immersed in a vessel in which dry ice was added to decyl alcohol for cooling. 62.02 g (23 8 mmol) of the bis(gas carbonyl) tricyclic ring produced in Reference Example 2 [5, 2, 1, 02 '6] decane was dissolved in 186 g of γ-butyrolactone, kept at 5 to -20 ° C and added dropwise to the reaction vessel over 60 minutes. After the dropwise addition, the reaction vessel was immersed in an ice bath. It was kept at 0 to 10 ° C and stirred for 2 hours. Further, 12.5 g (158 mmol) of pyridine was added. The reaction solution was returned to room temperature, and 12.312 g (75 mmol) of 5-norbornic acid needle and 5.93 were added. g (75 mmol) D is set to σ, immersed in a hot water bath at 50 ° C, and the reaction solution is stirred at 50 ° C for 18 hours. 140356.doc -58 - 201011465 In the above reaction solution After ethanol was introduced, the polymer was precipitated and recovered, and dissolved in 470 g of GBL. Then, ion exchange was carried out with 78 g of a cation exchange resin and 95 g of an anion exchange resin. The solution was added dropwise under high-speed stirring. In 5 to 5 L of ion-exchanged water, the polymer is dispersed and precipitated, and after appropriate washing with water and dehydration, vacuum drying is performed to obtain an aqueous solution-soluble polymer (P-3) containing a PBO precursor unit. The weight average molecular weight of the alkaline aqueous solution-soluble polymer measured by GPC is a single steep curve in terms of polystyrene of 29300. The analysis conditions of GPC are as follows. Column: manufactured by Showa Denko, Trade name Shodex 805M/806M tandem eluent: N-methylpyrrolidone, 40 ° C Flow rate: 1.0 ml / min Detector: manufactured by JASCO Corporation, trade name RI-930 [Reference Example 6] &lt;Naphthalene Synthesis of Megurodiazide Compound&gt; 109.9 g (0.3 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to a separable flask having a capacity of 1 L. 330 g of tetrahydrofuran (THF) and 47.5 g (0.6 mol) of 1 bit ratio, and added 98.5 g (0.6 mol) of 5-northene-2,3-dicarboxylic acid liver to the powder at room temperature. The reaction was carried out for 3 days at room temperature, and the reaction was confirmed by HPLC (high performance liquid chromatography). As a result, the starting material was not detected at all, and the product was a single peak with a purity of 99%. Was detected. The reaction solution was directly added dropwise to 1 L of ion-exchanged water under stirring, and the precipitate was separated by filtration, and then 500 140356.doc -59 - 201011465 ml of THF was added thereto and stirred to dissolve, and then the homogeneous solution was filled with 1% of the 1% ion-replaced resin: Amberlyst 15 (manufactured by Organo Company) glass column 'to remove the remaining pyridine. Then, the solution was precipitated by dropwise addition of 3 L of ion-exchanged water under high-speed stirring, and the mixture was separated by filtration and vacuum-dried. The ruthenium imidization of the product was confirmed by the following cases: the characteristic absorption of the quinone imine group at 1394 cm·1 and 1774 cm·1 in the IR spectrum, and at 1540 cm·1 and 1650 cm· There is no characteristic absorption of the guanamine group in the vicinity of 1, and there is no peak of protons of guanamine and carboxylic acid in the NMR spectrum. Then, 65.9 g (0.1 mol) of the product, 53_7 g (〇.2 m〇l) of 1,2-naphthalene-separated gas 4-continued gas and 560 g of acetone were added under 2〇. Mix and dissolve. 21 2 g (〇 21 mol) of triethylamine was diluted with 106.2 g of acetone at a fixed rate for 30 minutes. At this time, the reaction liquid is subjected to temperature control in the range of 20 to 30 Torr using an ice water bath or the like. After the completion of the dropwise addition, the temperature was further increased to 20. (: After stirring for 30 minutes, 5.6 g of a hydrochloric acid aqueous solution having a concentration of 36% by weight was then added, and then the reaction liquid was cooled by an ice water bath. The precipitated solid matter was subjected to suction and subtraction separation. The filtrate obtained at this time was added dropwise to a hydrochloric acid aqueous solution having a concentration of 0.5 mass%/〇 under agitation for 5 hours, and the target product was precipitated, and subjected to suction filtration separation to recover the obtained cake. The material was again dispersed in 5 L of ion-exchanged water, stirred, washed, separated by filtration, and the water washing operation was repeated 3 times. The finally obtained cake was vacuum dried at 4 ° C for 24 hours to obtain a photosensitive film. Sex diazonium compound (Q-1) 140356.doc • 60-201011465 [Reference Example 7] 3 〇g (〇〇7〇7 m〇1) was added to a separable flask having a grain size of 1 L a compound of 4,4,-(1_(2_(4-hydroxyphenyl))propyl)phenyl)ethylidene bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Tris_PA) as a polyhydroxy compound, Adding 1,2-naphthalene equivalent to 83 3 moles of its oh group醌Diazide _4_sulfonyl chloride 47 49 g (〇177 m〇1) After stirring the solution obtained by dissolving in 300 g of acetone, the flask was adjusted to 30 °C by a thermostatic bath. Then, 17_9 g of triethylamine was dissolved in 18 g of acetone, and after being placed in a dropping funnel, it was added dropwise to the flask over 30 minutes. After completion of the dropwise addition, stirring was continued for further 3 minutes, and then hydrochloric acid was added dropwise thereto, and the mixture was further stirred for 3 minutes to complete the reaction. Thereafter, triethylamine hydrochloride was removed by filtration. The filtrate obtained here was added dropwise to a beaker which was stirred and mixed with pure water of 64 g of hydrazine and 30 g of hydrochloric acid to obtain a precipitate. The precipitate was washed with water and filtered, and then dried under reduced pressure of 4 ° C for 48 hours to obtain a photoacid generator (Q-2). [Reference Example 8] A glass separable three-necked flask equipped with a tin-type stirrer made of Teflon (registered trademark) was used as a reaction container. To the reaction bar, 131.0 g of dibutyl succinate dihydrate and γ-butyrolactone of g were added thereto, and 132.8 g of 3-aminopropyl group was slowly added dropwise thereto at room temperature. A solution of triethoxy zebra and 27 g of γ-butane vinegar. As the dropwise addition progresses, the reaction solution heats up to about 4 Torr, and as the reaction progresses, the peak recognizes the generation of carbon dioxide. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then the reaction liquid was subjected to high performance liquid chromatography (HPLC) for 140356.doc-61-201011465, and the raw material was not detected at all, and the product was inflamed. The purity of the material was detected as an early peak value of 98%. Thus, a solution of the auxiliary agent was obtained. &lt;Preparation of photosensitive resin composition&gt; [Examples 1 to 13 and Comparative Examples 1 to 14] 100 parts by mass of the hydroxypolyamines (P-1, P-2, P-3) obtained in the above Reference Example 3, Reference Example 4, and Reference Example 5, and the above-mentioned Reference Examples 6 and 7; The nitrogen-containing compound (Q-), q_2), and the following unsaturated compound of C1~ci〇 are dissolved in 170 to 220 parts by mass of gB1, and then 30 parts by mass of the subsequent auxiliary agent obtained in Reference Example 8 is added. The filter of 〇2 μηη was filtered to prepare the photosensitive tree deer composition of Examples 丨 to 3 and the comparative examples 1 to 14 shown in Table 1 below. (Cl) ΒΑΝΙ-Μ (Maruzen Petrochemical: Trade Name (C-2) ΒΑΝΙ-Η (Maruzen Petrochemical: Trade Name) (C-3) BANI-D (Maruzen Petrochemical: Trade Name) (C-4) Β ΑΝΙ-Χ (Maruzen Petrochemical: trade name) (C-5) Tetraallyl phthalate (C-6) Triallyl trimellitate (C-7) Trimethylolpropane III Methacrylate (C-8) &gt;1,:^'-1,3-Extended Dimethyleneiminimide (C-9) 4,4'-bis-xetylenediimide Diphenyl decane (C-1 fluorene) bis(3-ethyl-5-fluorenyl-4-maleimido phenyl) decane &lt;Evaluation of photosensitive resin composition&gt; (1 ) Evaluation of patterning characteristics and preparation of pre-baked film and film thickness measurement 140356.doc • 62· 201011465 The photosensitive resin combination of the above examples and comparative examples was combined by a spin coater (Clean Track Mark 8 manufactured by Tokyo Electron Co., Ltd.) The object was spin-coated on a 6-inch wafer and pre-baked on a hot plate at 125 ° C for 180 seconds to obtain a film for evaluation. The initial film thickness of each composition was adjusted so as to be 320 ° C. The resin film thickness after hardening for 1 hour was 7 μm. The film thickness was measured by a film thickness measuring device (Lambda ACE manufactured by Dainippon Screen Manufacturing Co., Ltd.). • Exposure to the film, By attaching a test chart The mask of the case was exposed using a stepping machine (NSR2005i8A manufactured by Nikon Corporation) having an exposure wavelength of i line (365 nm) to gradually change the exposure amount. • Developing a developer using the developer (AZ Electronic) AZ300MIF developer manufactured by Materials, 2.38 mass% of tetrakis ammonium hydroxide aqueous solution) was developed at 23 ° C to adjust the development time so that the film thickness after development reached 85% of the initial film thickness. Then, it is rinsed with pure water to form a positive relief pattern. • Production of cured film Then, the film after development was cured at 320 ° C for 1 hour using a temperature-increasing supply box (VF200B manufactured by Koyo Thermo System Co., Ltd.) to prepare a cured film. In Comparative Examples 5 to 8, 12, and 13, foreign matter was observed on the prebaked film. Further, the sensitivity of the photosensitive resin composition, the pattern shape at the time of curing, the cured residual film ratio, the adhesion, and the development residue were evaluated as follows: 140356.doc -63 - 201011465. The results are shown in Table 2 below. [Sensitivity (mJ/cm2)] The minimum exposure amount at which the exposed portion of the coating film can be completely dissolved and removed under the film thickness after development. [Pattern shape after curing (evaluation by taper angle)] A section of the 5 〇 μιη line after curing was observed using a S-2400 type Hitachi scanning electron microscope manufactured by SigmaZONE. In this cross section, as shown in Fig. 1, the angle formed by the pattern side surface of the line and the substrate is determined as a taper angle. If the 锥 cone angle is 5 〇. When it is 1, it can be judged as a surface protective film and an interlayer insulating film which are suitable as a semiconductor device. [Cured residual film rate] (cured film after curing, film 彳 彳 厚 厚 χ χ χ χ 膜 膜 〇〇胄 〇〇胄 〇〇胄 〇〇胄 〇〇胄 〇〇胄 Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ The exposure and exposure of the Qiu Φ RUN &amp; 2 times the exposure amount of the exposure of the Ρ 中 显影 显影 显影 线 ^ ^ pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm pm The residual component (developing residue) at the time of development of the display (d) obtained under the above conditions. Whether or not the residue is observed on the surface, C: the entire surface A: none (good), B: - the developing residue was observed on the part _. H0356.doc • 64 - 201011465 [Table i] (A) (B) (C) Example 1 P-1 Ql (18 parts by mass) Cl (10 parts by mass) Example 2 P-1 Ql (18 parts by mass) C-2 (10 parts by mass) Example 3 P-1 Q1 (18 parts by mass) C-3 (10 parts by mass) Example 4 P-1 CH (18 parts by mass) C-4 (10 parts by mass) Example 5 P-1 Ql (18 parts by mass) C-4 (4 parts by mass) Example 6 P-1 Q-1 (18 parts by mass) C-4 (20 parts by mass) Example 7 P-1 Q-1 (14 parts by mass) C-4 (20 parts by mass) Example 8 P-2 Q-2 (20 parts by mass) Cl (10 parts by mass) Example 9 P-2 Q-2 (20 parts by mass) C-3 (10 parts by mass) Example 10 P-2 Q-2 (20 parts by mass) C-4 (10 parts by mass) Example 11 P-2 Q1 (20 parts by mass) C-4 (10 parts by mass) Example 12 P-3 Q -2 (12 parts by mass) C-4 (10 parts by mass) Example 13 P-3 Q-2 (20 parts by mass) 04 (10 parts by mass) Comparative Example 1 P-1 Ql (18 parts by mass) No comparative example 2 P-1 Ql (18 parts by mass) C-5 (10 parts by mass) Comparative Example 3 P-1 Ql (18 parts by mass) 06 (10 parts by mass) Comparative Example 4 P-1 Ql (18 parts by mass) 07 ( 10 parts by mass) Comparative Example 5 P-1 Ql (18 parts by mass) C-8 (10 mass) Comparative Example 6 P-1 Q1 (18 parts by mass) 09 (10 parts by mass) Comparative Example 7 P-1 Q1 (18 parts by mass) C-10 (10 parts by mass) Comparative Example 8 P-1 Q1 (18 parts by mass) C-10 (20 parts by mass) Comparative Example 9 P-2 Q-2 (20 parts by mass) No Comparative Example 10 P-2 Q-2 (20 parts by mass) C-6 (10 parts by mass) Comparative Example 11 P -2 Q-2 (20 parts by mass) 07 (10 parts by mass) Comparative Example 12 P-2 Q-2 (20 parts by mass) 08 (10 parts by mass) Comparative Example 13 P-2 Q-2 (20 parts by mass) C-10 (l () parts by mass) Comparative Example 14 P-3 Q-2 (20 parts by mass) None 140356.doc -65- 201011465 [Table 2]

Sensitivity cone angle curing residual film rate adhesion (μιη) Development residue Example 1 360 65 79.7 3.5 Dissolution Β Example 2 230 54 79.4 4.0 Dissolution A Example 3 240 52 79.1 3.0 Dissolution A Example 4 220 58 79.7 2.0 Dissolution A Example 5 270 52 78.7 3.5 Dissolution A Example 6 200 69 80.5 1.5 Dissolution A Example 7 210 71 80.7 1.5 Dissolution A Example 8 320 59 75.3 4.0 Dissolution B Example 9 200 54 74.7 5.0 Dissolution A Example 10 180 57 75.3 3.5 Dissolution A Example 11 200 58 76.0 2.5 Dissolution A Example 12 170 61 78.1 3.0 Dissolution A Example 13 190 59 77.5 2.5 Dissolution A Comparative Example 1 400 42 78.0 18 Exfoliation A Comparative Example 2 300 47 78.6 10 Exfoliation A Comparative Example 3 250 45 78.2 11 Peeling off A Comparative Example 4 250 52 81.2 18 Peeling off A Comparative Example 5 500 54 79.4 7.0 Peeling off C Comparative Example 6 500 58 79.2 9.0 Peeling off C Comparative Example 7 450 56 78.9 8.0 Peeling off C Comparative Example 8 510 66 80.1 7.0 flaking C Comparative Example 9 360 37 73.6 20 flaking A Comparative Example 10 210 40 73.8 12 flaking A Comparative Example 11 200 50 77.0 20 flaking A Comparative Example 12 460 53 75.1 10 Peeling C Comparative Example 13 410 52 74.5 8.0 Peeling C Comparative Example 14 370 39 75.1 17 Peeling A

[Industrial Applicability] 140356.doc -66 - 201011465 The photosensitive resin composition of the present invention can be suitably used as a surface protective film for a semiconductor device, an interlayer insulating film, and an insulating medium for rewiring and protection for a flip chip device. A film, a protective film of a device having a bump structure, an interlayer insulating film of a multilayer circuit, a protective film of a flexible copper box, a solder resist film, a liquid crystal alignment film, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a 50 μm line of a cured embossed pattern observed by a s_24 曰 type scanning electron microscope manufactured by Sigma Industries, Inc. [Description of main component symbols] (a) Substrate surface (b) Pattern side of surface protection film Θ Cone angle 140356.doc -67-

Claims (1)

201011465 VII. Patent application range: 1. A photosensitive resin composition characterized by having an alkaline aqueous solution soluble polymer having a hydroxyguanamine structure represented by the following formula (1). The mass part includes (B) 1 to 50 parts by mass of the photoacid generator, and (C) 1 to 40 parts by mass of the compound represented by the following formula (2): [Chemical Formula 1] Wherein X! is a tetravalent organic group having at least 2 carbon atoms, Y1 is a divalent organic group having at least 2 carbon atoms, and is called an integer of (7) (10)}; [Chemical 2] Wherein ' 01 has at least one functional group selected from the group consisting of a hydrogen atom, a carbon number of 1 to 6, an alkenyl group, and a crosslinkable organic group, and is represented by a group selected from -CH2·, -Ο - and -S- are groups in the group, Ζι is a divalent organic group, ηι is an integer from 0 to 4, and when there are plural 〇1, plural Di may be the same or different}. 2. The photosensitive resin composition of claim 1 wherein (B) the photoacid generator is a compound having a naphthoquinonediazide structure. The photosensitive resin composition of claim 1, wherein the compound represented by the formula (2) is selected from the group consisting of compounds represented by the following formula (3): 3] 4. The photosensitive blush composition of claim 1, wherein (A) the alkali aqueous solution-soluble polymer having the hydroxyguanamine structure represented by the general formula (1) has a structure represented by the following formula (4): 140356 .doc -2· (4) 201011465 [Chemical 4] Ο (5) At least one of L2 and L3 methyl groups or a group consisting of the structures shown, the work independently represents a hydrogen atom 戍 ΒΤ main-cadaveric group, and L4 represents a hydrogenogen 4 base}. 5. The photosensitive resin composition of claim 1, wherein (4) the end of the soluble polymer having the structure of the base (4) represented by the formula (1) is selected from the group consisting of the following formula (6); By: [Chem. 6] In the formula, L5 represents 140356.doc 201011465 base ' and L6 represents a wind atom or a burnt group} in a group consisting of -CH2-, _〇_, and _s_. 6. A method of manufacturing a hardened relief pattern And characterized in that it comprises the steps of: (1) forming a photosensitive resin layer containing the photosensitive resin composition according to any one of claims 1 to 5 on a substrate; (2) exposing with actinic rays via a photomask Or directly irradiate the light or the illuminating part to accommodate or remove; • an electron beam or an ion beam; (3) heating the exposed portion (4) to the resulting embossed pattern. 7. A semiconductor device having a cured embossed pattern. As requested in item 6, I40356.doc