TW200940601A - Precursor for heat-resistant resin and photosensitive resin composition containing the same - Google Patents

Abstract

An alkali-soluble resin is provided which contains no halogen atom in the molecule, has high sensitivity, and attains a wide margin of film thickness in pattern formation conducted using the same exposure amount and the same development period. The resin can be developed with the developing solution in general use in semiconductor device production steps (2.38% aqueous TMAH solution), is soluble in γ -butyrolactone, and is suitable for use in photosensitive resin compositions. This resin has, in the molecule, a structure represented by general formula (1): {wherein X1 represents a tetravalent organic group containing no halogen atom; and Z1 represents a divalent organic group represented by general formula (2): (wherein L1, L2, and L3 each independently represents hydrogen or methyl and L4 represents hydrogen, methyl, or hydroxy)}.

Description

[Technical Field] The present invention relates to an alkali-soluble resin and a positive or negative photosensitive resin composition containing the alkali-soluble resin, which is used to form an electronic component. Or an insulating material of the display element, and an undulating pattern of a heat resistant resin material used in a passivation film, a buffer film, an interlayer insulating film, or the like in a semiconductor device. [Prior Art] Among the applications of the surface protective film or the interlayer insulating film of a semiconductor device, a polyacrylonitrile resin having excellent heat resistance, electrical properties, and mechanical properties is widely known. The polyiminoimide resin used for this purpose is generally provided in the form of a photosensitive polyimide intermediate composition composition, which is applied to a substrate such as a dream wafer, and is sequentially subjected to pattern exposure by active light. And development, and thermal imidization treatment, whereby a heat resistant resin film having a fine undulating pattern can be easily formed on the substrate. However, 'in the case of using the above-mentioned photosensitive polyimideimine precursor composition®, 'in its development step' requires the use of a large amount of organic solvent as a developing solution, in terms of cost, safety, and concern for environmental problems in recent years. In terms of upswing, countermeasures for removing organic solvents are required. For this reason, various heat-resistant photosensitive resin materials which can be developed with a dilute alkaline aqueous solution in the same manner as the photoresist have recently been proposed. Recently, attention has been paid to polyhydroxyguanamines which are soluble in dilute alkaline aqueous solutions, namely polybenzoxazoles (hereinafter also referred to as "pB〇j" precursors and photosensitive diazonaphthoquinone compounds (hereinafter also A photosensitive resin composition (hereinafter referred to as "PAC") having a photoactive activity (hereinafter referred to as "PAC"), such as "NQD", is used in practice. In addition, as a heat-resistant photosensitive resin composition which can be developed with a rare aqueous solution, a combination of an alkali-soluble resin having a phenolic hydroxyl group introduced into a side chain and PAC, and a combination thereof are also proposed. A majority of the skeleton, such as a combination of a polyamidene-PBO precursor polymer and a PAC, which is obtained by using trimellitic acid to form a polyimine imine precursor unit and a PBO precursor unit alternately. In the above-mentioned heat-resistant photosensitive resin composition, the alkali-soluble resin used in combination with pAC is mainly a polyamine having a phenolic hydroxyl group such as a polyacrylimide precursor or a PBO precursor. By introducing the phenolic hydroxyl group into the polymer skeleton, the exposed portion is dissolved in the dilute alkaline aqueous solution during development, and the unexposed portion is dissolved by the interaction between the desired trans group and the PAC, thereby being inhibited. Form a positive relief pattern. As a method for introducing human (4) in a polymer, an aromatic diamine having an ortho-group and a phenolic hydroxyl group (hereinafter also referred to as "phenolic diamine") is generally used as a polyamine. The original #, and it is dehydrated and condensed with the carboxylic acid. (4) When the acidity of the rhodium group of the diamine is low, the polyamine is insoluble in the dilute alkaline aqueous solution, and the residual residue of the exposed portion is generated during development, or the development itself cannot be achieved. On the other hand, in the case where the acidity of the base of the diamine is higher, the interaction with the PAC is weak, and the unexposed portion is also dissolved during development, and a high-quality undulating pattern cannot be obtained. As an amine 2,2-bis(3-amino-4-trans-phenyl)hexafluoropropane which is excellent in the balance of the acidity and transparency of the amine group, it is now widely used as a positive type. The phenolic diamine of the photosensitive resin composition was 136,993.doc 200940601. However, in recent years, materials which do not contain a halogen atom such as a fluorine atom have been strongly demanded due to an increase in reliability of a semiconductor device and environmental considerations. Further, in the exposure step in the manufacture of a semiconductor device, a reduced projection exposure machine called an i-line stepper using an i-line having a mercury lamp is mainly used. The stepping machine is a very expensive machine, so if the photosensitive resin composition is low in sensitivity, the exposure time required to form the undulating pattern becomes long, and the number of stepping machines required increases, resulting in a high exposure process. Cost. Therefore, it is strongly required to increase the light sensitivity of the photosensitive resin composition. In the ® positive photosensitive resin composition, in order to improve the light sensitivity, it is first necessary to increase the penetration of the i-line of the polymer without hindering the decomposition of the PAc of the exposed portion. Therefore, for the polymer used in the positive photosensitive resin composition, it is required to improve the i-line permeability. Further, the stronger the interaction between the phenolic hydroxyl group of the polymer and pAC, the greater the difference in the dissolution rate of the unexposed portion and the exposed portion to the alkaline developing solution, and as a result, the light sensitivity is high. Therefore, the polymer used for the positive photosensitive resin composition is required to have a strong interaction with pAC. ◎ On the other hand, in recent years, as a ♦ agent for a heat-resistant photosensitive resin composition, there is a guanamine-based solvent such as ketopyrrolidone which is more alkaline, and more preferred is vinegar. The tendency of a neutral solvent or the like is exemplified as a solvent which is urgently required for a semiconductor manufacturing step. Therefore, for the polymer used in the positive photosensitive resin composition, it is required to be dissolved in 丫-butyrolactone. Further, as a rare developer which is used for forming a pattern by using a heat-resistant photosensitive resin composition, it is usually used in a semiconductor manufacturing step of 2.38 weight/. The tetramethylammonium hydroxide aqueous solution (hereinafter also referred to as "2"% τμαη 岭液)" is strongly required to be developed by 136993.doc 200940601 in a 2 3 aqueous solution. Further, in the manufacturing process of the semiconductor device, since the germanium wafer to which the photosensitive composition for protective film is applied is formed with a wiring circuit or an external connection terminal, the surface is uneven. When the photosensitive resin composition is applied to the ?? shape of the tantalum wafer on which the wiring circuit or the external connection terminal is formed, the film thickness of the photosensitive resin composition layer becomes uneven in the wafer surface. . In the photosensitive resin composition for a general protective film, when the film thickness to be applied is changed, there is a problem in that it is necessary to change the exposure amount and development time required for the pattern to be changed, and the film thickness changes. In the case of the pattern forming process, the margin is narrow. In the case of &, a photosensitive resin composition having a wide film thickness at the time of patterning with the same exposure amount and the same development time is strongly required. The present inventors have proposed a positive photosensitive resin composition (hereinafter referred to as Patent Document 2) which uses a bis (3-amino-4-hydroxyl group) having a higher acidity of a phenolic hydroxyl group as a hard substitute for a fluorine atom. _Bis(3-amino-4-yl-phenyl)hexapropene 9' is used as a ruthenium precursor containing no i atom in the molecule, and comprises a condensate of the ruthenium precursor with a monocarboxylic acid and pAc. However, in the example of Patent Document 2, 'dicarboxylic acid is a compound having a fluorine atom, and further, the developer is not an aqueous solution of TMAH used in a semiconductor manufacturing step, but using a 0.79% TMAH aqueous solution. . It is generally considered that the purpose of sx or the like is to control the solubility of a stronger polymer derived from bis(3-amino-4-yl)-hydroxyl group. The inventors of the present invention synthesize a condensate containing a functional atom described in Patent Document 2 as an acid, and an oxydiphenyl acid and a bis(3.amino-4-yl-phenyl) condensate. At the time, the polymer obtained by the 136993.doc 200940601 is insoluble in γ-butyrolactone, and has high transparency to the i-line, but has low interaction with the PAC, and thus is not sufficient for satisfying the light sensitivity.

A positive photosensitive resin composition containing a solvent-soluble polyimine containing a phenolic hydroxyl group and a PAC containing no halogen atom in the molecule has been proposed (hereinafter referred to as Patent Document 3). Patent Document 3 describes a polymer having a tetrarubic acid containing a bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetradecanoic acid dianhydride. a polycondensate of a structure obtained by dehydration condensation of an anhydride with an aromatic diamine containing bis(3.amino)-4-hydroxyphenyl)sulfone, in the case of obtaining a polycondensate, combining all tetracarboxylic dianhydrides with In all the raw material monomers obtained from all the aromatic diamines, the bis(3-amino-4-phenylphenyl) group is in the range of 2 〇 mol% to 40 mol% when the raw material is added to obtain a polycondensation. The ratio of the molar number of all tetracarboxylic dianhydrides to the molar number of all aromatic diamines is 1: 〇75~〇87 or 0.75~0.87:1, and the weight average molecular weight of the polycondensate is at A range of 5,000 to 17,000. Patent Document 3 discloses a positive photosensitive resin composition containing no halogen atom by using bis(3-amino-4-phenylphenyl)anthracene in a phenolic diamine. The molecule does not contain a tooth atom and exhibits the interaction between alkali solubility and PAC. By using bicyclo(2,2,2)-octyl-7-ene 2,3'5,6-tetracarboxylic acid di-hepatic, the γ is increased. - solubility of vinegar and i-line transparency 'by controlling the amount of bis(3.amino phenyl phenyl) and the weight average molecular weight' is controlled by bis(3_amino-o-phenyl) The hard base is 'cohesive' and the positive photosensitive resin composition is soluble in γ· 丁, which is sufficiently transparent to the 1 line and can be patterned with a 2.38% TMΑΗ developing solution. However, the introduction amount of bis-amino-4 phenylidene phenyl stone is limited by the height of the solution of 136993.doc 200940601, so the density of the (4) warp group in the polymer decreases. The (3.Amino-4)-phenylphenyl) hard hetero group has a weak interaction with pAc, and therefore a positive photosensitive resin composition having higher sensitivity is desired. In the following Patent Document 4, it is disclosed that an alicyclic dibasic acid and a diamine are included; a PBO precursor, as a preferred second (four), is described as a cyclohexanol acid, which is disclosed in Example 3. There is a positive photosensitive resin composition n-form which is obtained by dissolving a polycondensate containing no tooth atoms in a molecule in N_methyl_2_対, in 2, 2 bis (3_amino group _ 4_ The condensate of the benzoyl fine and the cyclohexanal acid, the polycondensate is insoluble in the γ-butane vinegar, and 'cannot sufficiently satisfy the positive photosensitive resin composition degree. ' ❹ - other than this 'As a precursor to the use of an alicyclic dicarboxylic acid, the following Patent Documents 5 to 7 are not disclosed, but it is generally considered that the following polymer has not been provided, that is, it does not contain a tooth atom in the molecule, and is dissolved in γ_ Internal vinegar, and the photosensitive resin composition thereof has high sensitivity, and has a wide film thickness at the same exposure amount and the same development time. 2 $ In the following Patent Document 8, it is disclosed that The heat-resistance of the tricyclic ring from the structure of the money structure is disclosed in Patent Document 9 below, which discloses that it is a gas barrier film. In the field of a polybenzoxazole resin having a tricyclodecane structure, and in the following patent document, a compound containing an acid generated by a ruthenium precursor resin and radiation is disclosed, and A negative-type photosensitive resin composition of the compound which cross-links by the action of the acid. 136993.doc 200940601 [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. 119-426 [Patent Document 3] International Publication No. 7/〇29614 [Patent Document 4] Japanese Patent Laid-Open Publication No. Hei 2 No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 9] Japanese Patent No. 3966590 (Patent Document 10) [Problems to be Solved by the Invention] An object of the present invention is to provide an alkali-soluble resin as Photosensitive resin composition When there is no tooth atom, the film thickness is wide at the same exposure amount and the same development time, and the film thickness is wide, and the sensitivity is high, and the developing solution generally used in the manufacturing process of the semiconductor device can be used (2·38). Weight: tetramethylammonium hydroxide aqueous solution) to form a pattern, soluble in γ-butyrolactone solvent. Further, it is an object of the present invention to provide a method for forming a hardened relief pattern on a substrate using the composition, and having the hardening A semiconductor device in which a undulating pattern is formed. [Technical means for solving the problem] In order to solve the above problems, the inventors of the present invention condensed water by removing water from a phenolic diamine containing no atom and an aromatic dicarboxylic acid. The polyamines (ruthenium precursors) containing the desired transradicals were studied. The result is 136993.doc -12- 200940601 The resin with specific structure is soluble in γ-butyrolactone, which has high transparency to the i-line of mercury lamp, and the interaction with PAC is strong enough and has high sensitivity. Therefore, a positive photosensitive resin composition containing no tooth atoms in the alkali-soluble resin molecule can be obtained. The positive photosensitive resin composition using the alkali-soluble resin was studied, and as a result, the present invention was completed.

Further, 'the compound which generates an acid by irradiation with active light and the compound which can be crosslinked by the action of an acid are combined with the resin of the present invention to carry out a study. As a result, a negative photosensitive resin composition which solves the above problems can also be obtained. 'Therefore completing the invention. That is, the present invention is specifically as follows. [1] A resin having a structure represented by the following formula (1) in a molecule: [Chemical Formula 1]

Ο II i?

OH

HN-Xi-NH-C-Zi-C- OH

In the formula {wherein, X represents a tetravalent organic group which does not contain a halogen atom, and z represents a divalent organic group represented by the following formula (2): [Chemical 2]

(In the formula, 'Li, L2 and L3 each independently represent a hydrogen atom or a fluorenyl group, and [Table 136993.doc • 13-200940601 shows a hydrogen atom, a methyl group or a hydroxyl group)}. [2] A resin having a structure represented by the following formula (3) in a molecule: [Chemical 3]

(ε) {wherein, 乂1 and 乂2 represent a tetravalent organic group which does not contain a halogen atom, and may be the same or different, and the core represents a divalent organic group represented by the following general formula (2): ]

136993.doc -14- 200940601 (wherein, L, L2 and L3 each independently represent a hydrogen atom or a fluorenyl group, and ^ represents a hydrogen atom, a methyl group or a hydroxyl group), and & represents a non-purine atom having an aromatic ring. A divalent organic group, mi represents an integer of ^200, & represents an organic group having a 2 to 4 valence of a tooth atom, & represents a tetravalent organic group which does not contain a halogen atom, and 叱 and 叫 respectively represent 〇~200 The integer is called an integer representing 〇~2 and is called an integer of 〇~1, and the arrangement order of each unit of mi, calling, and calling is not limited}. m is a resin of the above π] or [2] which has a structure represented by the following formula (4): [Chemical 5]

In the formula, RjR277 is independently a group selected from the group consisting of a hydrogen atom and a benzene ring in which 碳L:T is substituted with a carbon number of 1 to 6, and r-group}〇. iR3 and R4 are each independently a hydrogen atom or an organic group having a carbon number of 1 to 4 = (1) or [2], which is represented by the following (10), and is represented by

~Q〇i 136993.doc •15· (5) 200940601 [5] Resin structure as described above] or [2]: [Chemical 7] It has the formula (6)

[6] The resin according to the above [1] or [2], which has a structure represented by the following formula (7): [Chem. 8]

[7] The resin of [n or [2] above, which has a formula represented by the following formula (8)

Structure: [Chemistry 9]

[8] as described in the above formula (9) as described above [η or the resin, which has the structure: 136993.doc -16- 200940601 [化 ίο]

[9] The structure of the resin of the above [丨] or [2]: which has the formula (10): [Chemical Formula 11] ❹

—NH-HO (10) {wherein, the R-based carbon number is 1 to 4 one-valent organic group}. [10] The resin according to the above [1] or [2], which has a structure represented by the following formula (11): [Chem. 12]

[11] The resin according to the above [1] or [2], which has a structure represented by the following formula (12): [Chem. 13]

(1 2) 〇 136993.doc -17· 200940601 [12] The structure of the resin of the above Π] or [2]: which has the following formula (13) [Chem. 14]

ΟΗ (1 3) 〇❹ [13] The resin of the above [2] wherein Z2# in the above formula (3) is at least one selected from the group consisting of the following structural formula (10): ]

In the formula, L5 is selected from the following valence groups of organic groups: [Chem. 16]

(wherein, L6 represents a monovalent alkyl group having a carbon number of 1 to 4)}. [14] The resin according to the above [2], wherein the mono-l-containing moiety containing the polyamidino group in the above formula (3) has a group selected from the group consisting of the following formula (15) and the following formula (16) At least one structure in the middle: 136993.doc 200940601 [Chem. 17]

[15] The resin according to any one of the above [1] to [14], which is selected from the group consisting of the following structures, wherein at least one terminal group of the terminal of the resin is

[16] A positive-type photosensitive resin composition containing the alkali-soluble resin of the resin according to any one of the above (1) to [15], which contains 1 to 100 parts by mass of (4). B) Photosensitive diazonaphthoquinone compounds. [17] The positive photosensitive resin composition of the above [16], which further contains 100 to 2000 parts by mass of the (C) organic solvent. [18] The positive photosensitive resin composition according to the above [16] or [17] wherein (B) the photosensitive diazonaphthoquinone compound is selected from the group consisting of polyhydroxy compounds represented by the following formula: 7) , 2-naphthoquinonediazide-4-sulfonate, and the group consisting of 1,2-naphthoquinonediazide-5-ylidetate of the compound 136993.doc •19-200940601 base compound At least one compound: [Chem. 19] Ο

[19] The positive photosensitive resin composition of the above [17], wherein (c) the organic solvent is γ-butyrolactone. [20] as described in [16] above. The positive photosensitive resin composition of any one of [19] further contains 0.01 to 20 parts by mass of the (D) alkoxydecane compound. [21] The positive photosensitive resin composition of the above [20] Wherein (D) the pyrithione decane compound is at least one compound selected from the group consisting of compounds represented by the following general formulae (18) to (25): [Chem. 20]

H〇_U (18) {wherein, X and s represent 1 and X2 represents a divalent organic group, an integer of 0 to 2}; X3 and X4 represent a monovalent organic group 136993.doc • 20- (19) 200940601 [ 21] (x5)s η ο

(X6-0)3.s-Si-X7-NC^x/COOH HOOC^ Ν—X9-S1—(Ο—Xu)3-5 〇Η (X,〇)s { where Χ7&Χ9 indicates A divalent organic group, Χ8 represents a tetravalent organic group, Χ5, Χ6, Χίο, and Χιι are not monovalent organic groups, and s represents an integer of 0 to 2}; [Chem. 22] Γ^Ί

(Χΐ2)Γ·_ 4_ΝΗ—Χ)3—Si—(O—Xi5)3-S ^ k)s (20) where, Xi3 represents a divalent organic group, and X12, X14&X15 represents a monovalent organic group. , s represents an integer of 0 to 2, and t represents an integer of 0 to 5}; [Chem. 23] Ο Η

Xi6_C—N—Xj7—Si—(OX)9)3-s (2 1 ) (Xl8)s

{wherein, X〗 6 indicates -NH-R20 or -〇-Κ·21 (here, Κ·20 and R2 1 are monovalent organic groups which do not contain COOH groups); Χ17 indicates a divalent organic group, 18 and 乂19 represent a monovalent organic group, and s represents an integer of 0 to 2}; [Chem. 24] (2 2) HS—Χ22—Si—(〇X24)3-s (X23)s {wherein, x22 Indicates a divalent organic group, X23 and X24 represent a monovalent organic group, and s represents an integer of 0 to 2}; 136993.doc -21 - 200940601 [Chem. 25] H2N-C-NH-X25-Si-(0X27)3.5 〇(X26)s (2 3) {wherein, X25 represents a divalent organic group, X26 and X27 represent a monovalent organic group, and s represents an integer of 0 to 2}; [Chem. 26]

X29—X30—Si—(0X32)3^

(X3l)s (24) wherein x28 represents a hydrogen atom or a methyl group, and X29 is selected from a divalent group of the following formula: [Chem. 27]

-ch2- 0 II S〇2

ο 11 -〇—C_ΝΗ - Ο II

ο II -C-NH-Ο II -NH - C - NH - Ο II - c - ο - • ΝΗ - C - Ό - C - • Ο - C - C - NH - C CH3

X3G represents no divalent organic group 'X31 and X32 represent a monovalent organic group, s represents an integer of 0 to 2, and U represents an integer of 1 to 3}; and [Chem. 28]

\ J- 乂33—^34—Si—(OX36)3-S (2 5) (X35)s {wherein, X33 and X34 represent a divalent organic group, X35 and X36 represent a monovalent organic group, and s represents An integer of 0 to 2}. The positive photosensitive resin composition of any one of the above [16] to [21] further containing 5 to 20 parts by mass of (E) by heat a compound that reacts. [23] The positive photosensitive resin composition according to [22] above, wherein (e) the compound which causes a thermal father reaction by heat is selected from the group consisting of an epoxy group, a mercapto group, an alkoxymethyl group or At least one of a group consisting of a compound of oxetanyl and a bisallyl diimide compound. The positive photosensitive resin composition of any one of the above [16] to [23] further containing 1 to 30 parts by mass selected from the group consisting of (F) acrylate compound, methacrylate compound, and At least a seed of the group consisting of an allyl compound, a methoxy group-containing compound, and a phenyl ester compound. [25] The positive photosensitive resin composition according to any one of the above [16] to [24] further comprising 1 to 30 parts by mass of (G) an organic compound having a carboxyl group in the molecule. [26] A method of forming a hardening undulation pattern, comprising: applying a coating method of applying a positive photosensitive resin composition according to any one of φ [16] to [25] on a substrate, and performing the coating on the layer The exposure step of exposure, the development step of removing the exposure enthalpy/valley by the developer, and the heating step of heating the resulting undulation pattern. [27] A semiconductor device comprising a hardened relief pattern obtained by the method of forming [26] above. [A] a negative-type photosensitive resin composition comprising: (1) an alkali-soluble resin containing the resin of any one of the above (1) to [15], in an amount of 0.5 to 30 parts by mass ( H) A compound which can be crosslinked by the action of an acid by illuminating the active light to produce a compound of 136993.doc -23- 200940601 and 5 to 50 parts by mass of (1). [29] The negative photosensitive resin composition according to the above [28], wherein (1) the compound crosslinkable by the action of an acid is a compound having a methylol group or an alkoxymethyl group in the molecule. [3〇] A method of forming a hardening undulation pattern, comprising: a coating step of applying a negative photosensitive resin composition of the above [28] or [29] onto a substrate, and an exposure step of exposing the layer And a step of heating after the exposure, a developing step of eluting and removing the unexposed portion by the developing solution, and a heating step of heating the obtained undulating pattern. [31] A semiconductor device comprising a hardened relief pattern obtained by the method of forming [30] above. [Effects of the Invention] According to the present invention, it is possible to provide an alkali-soluble resin which does not contain a halogen atom in the molecule, and which has high sensitivity as a photosensitive resin composition, and forms a pattern with the same exposure amount and the same development time. The film thickness margin can be formed by the developer (2.38 wt% tetramethyl hydroxide aqueous solution) commonly used in the manufacturing process of the semiconductor device, and is soluble in T-butyl vinegar. Solvent. Further, according to the present invention, a method of forming a hardened relief pattern on a substrate using the composition and a semiconductor device having the hardened relief pattern can be provided. [Embodiment] First, the resin (a) of the present invention will be described. The resin (a) of the present invention is a tree having a structure represented by the following formula in the molecule: 136993.doc •24· 200940601 [Chem. 29]

-hn4Hn C—Zj-C 〇H

Ο II

ο II {wherein, Χα _ (1) The organic group of the formula (2), and 4 represents the following divalent organic group: [Chemical 3〇] ❹

(2) ❹ (Formula 2, Ll, which independently represents a hydrogen atom or a methyl group, and "Table π 虱 atom 'methyl or hydroxy)}. More repeating units. ^ The structure of the general formula (1) = single The resin (4) may have a solvent-soluble transbasic polyimine mono-' which may also have an organic thiol group represented by the following formula (3): 136993.doc •25· 200940601 [Chemical 3 1 ]

{式

Similarly, ΰ^1 and & represents a tetravalent organic group which does not contain a halogen atom, and may be different from each other, and represents a structure represented by the following formula (2).

(wherein, Μ, 1^ and B3 each independently represent a hydrogen atom or a methyl group, and ^ represents an ammonia atom, an yinyl group or a hydroxy group), and & represents a divalent organic group having an aromatic ring, and is represented by 1 An integer of ~2〇〇, & indicates not 3 _ original $ meaning atom 136993.doc -26- 200940601 2~4 organic group ' & represents a 4-valent organic group without tooth atom, milk and called independent An integer representing 0~2〇〇, called an integer representing 〇~2, is called 0~1 'here', ms, and the order of each unit is not limited}. The organic group represented by the above formula (2) is further preferably at least one selected from the group consisting of the following compound groups (a-1): [Chem. 33] Compound group (a-1)

Among these, especially the following compounds are more preferable: The resin (a) of the present invention will be described in detail below. In order to obtain the resin (a), a dicarboxylic acid having the structure of the above formula (2) and a diamine having a X! structure and a phenolic hydroxyl group can be used as a raw material. As a representative compound of the dicarboxylic acid having the structure of the above formula (2), bis(carboxy)tricyclo[mo2,6]nonane can be mentioned. The compound can be synthesized according to the synthesis method of the production example A of Japanese Patent Laid-Open Publication No. SHO-58-H0538, No. Sho-58-H0538, and the synthesis method of the embodiment of the patent specification No. 2002-504891. Obtained by the synthesis method of Synthesis Example 2 of the publication No. 09-15846. However, since this method uses heavy metals as the oxidizing agent, the following method is more preferable in that the metal is not used. In other words, a tricyclic (m,.) decane dimethanol (manufactured by Dongjo, Chemical Industry Co., Ltd. N〇τ〇85〇) was dissolved in acetonitrile or the like, and 2,2,6,6-tetradecylpiperidine was added. The catalyst such as oxygen free radical (hereinafter also referred to as "TEMPO") is adjusted to pH by using disodium hydrogen phosphate or sodium dihydrogen phosphate, and is added with sodium sulfite and sodium disulfite for oxidation and purification. This makes it possible to produce the target compound, namely bis(indenyl)=cyclo[5,2,1,〇2,6]decane. Further, the dicarboxylic acid compound having the structure of the above structural group (a) other than the above compound, methylcyclopentadiene dimer (manufactured by Tokyo Chemical Industry Co., Ltd. No. M0920), 1-meryl group II Cyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd. No. M〇910), 1-diyldicyclopentanyl (manufactured by Dongbu Chemical Industry Co., Ltd. No. H0684) as raw materials, by j. Ο 〇rg. A method known from Chem. 45, 3527 (1980), which adds hydrogen bromide or hydrogen chloride to the unsaturated bond of the above starting material, and is then known from j Am. Chem. Soc., 95, 249 (1973). In this way, carbon monoxide and water are further added, whereby two methyl groups can be introduced into the skeleton of the tricyclo[5,2,1,02 decane. As a method for synthesizing the dimethylol group, An intermediate is formed by adding 9-borobicyclo(3,3,1)nonane to an unsaturated bond by a method known in J. Am. Chem. Soc., 91, 2150 (1969). Thereafter, it is reacted with carbon monoxide to be reduced with LiALH(OCH3)3, and dimethylolmethyl hydrazine can also be produced by 136993.doc -28-200940601. According to the method for obtaining the dihydroxyindole substrate thus obtained when bis(carboxy)tricyclo[5,2,1,〇'6]nonane is obtained, the dimethylol group is similarly oxidized, whereby the target can be obtained. Dicarboxylic acid. In addition to the dicarboxylic acid having the structure of B1, it is also possible to copolymerize the two-reactive acid having the & structure as a z2 structure for the purpose of improving the mechanical elongation and improving the mechanical properties of the glass transition temperature. The second (four)' may be a divalent organic group having a tooth atom without an aromatic ring, preferably an aromatic dicarboxylic acid having a carbon number of 8 to 36, and an alicyclic ring having a carbon number of 6 to 34. At least one compound of the group consisting of dicarboxylic acids, for example, isophthalic acid, terephthalic acid, 4,4·-diphenyl phthalate, 3,4,-biphenyl bis Formic acid, 3,3,-diphenyl phthalic acid, Μ_naphthalene dicarboxylic acid, 2'3-naphthalene dicarboxylic acid, 1>5•naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, μ,·sulfonyl bisbenzene Formic acid, 3,4, sulfonyl bisbenzoic acid, 3,3, sulfonyl bisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4, oxybenzoic acid, 3, 3,-oxybisbenzoic acid, 2,2-double (4-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)propane, 2'2'-dimercaptophthalic acid, 3,3,_dimethyl-4,4, _Diphenylphthalic acid 2,2·-methyl-3,3'-biphenyldicarboxylic acid, 9,9-bis(4-(4-reaphenoxy)phenyl)anthracene, 9,9- Bis(4-(3-carboxyphenoxy)phenyl)anthracene, 4,4,_bis(4-carboxyphenoxy)biphenyl, 4,4ι_bis(3-carboxyphenoxy)biphenyl, 3 , 4,-dicarboxyphenoxy)biphenyl, 3,4'-bis(3-carboxyphenyloxy)biphenyl, 3,3,_bis(4-carboxyphenoxy)biphenyl, 3,3, - bis(3-carboxyphenoxy)biphenyl, 4,4,_bis(4-carboxyphenoxy)·terotriphenyl, 4,4 ι·bis(4-carboxyphenoxy)·crosslink 3 '4-Bis(4-reoxyphenoxy)_para-triphenyl, 3,3'-bis(4-reoxyphenoxy)-para-triphenyl, 3,4,-bis(4-carboxyphenoxy Base)-m-triphenyl, 3,3,_double 136993.doc •29· 200940601 (4-carboxyphenoxy)·m-linked triphenyl, 4,4,-bis(3-carboxyphenoxy couplet III Benzene, 4,4'-bis(3-sulfophenoxy)-m-triphenyl, 3,4,_bis(3 retinophenoxy)-pair triple stupid, 3,3· Bis(3-carboxyphenoxy)_para-triphenyl, 3,4,-bis(3-carboxyphenoxy)-m-triphenyl, 3,3·-bis(3-carboxyphenoxy)_ Biphenyl, Μ-cyclobutane dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ^-cyclohexanedicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, hydrazine, 3_phenylene Acetic acid, μ•phenylenediacetic acid, 5·aminoisophthalic acid derivatives in the pamphlet of International Publication No. 05/068535. In the case where the photosensitive resin composition is prepared, the solubility in 7-butyrolactone and the solubility in a dilute alkaline aqueous solution are preferably in the following formula (14). ) the compound represented: [Chem. 35]

(wherein 'Le denotes a valence alkyl group having a carbon number of 丨". When the resin (a) of the present invention is produced, the dicarboxylic acids may be used singly, and 136993.doc • 30· 200940601 may be combined 2 When the aromatic dicarboxylic acid is used for copolymerization, the i-line permeability of the mercury lamp is remarkably lowered. Therefore, the dicarboxylic acid having the Z2 structure is compared with the carboxylic acid having a & When the dicarboxylic acid having a structure + the diterpene acid having a Zz structure is set to 100 mol, the dicarboxylic acid having an A structure is preferably 10 to 100 mol, and the dicarboxylic acid having a Z2 structure is preferably a ruthenium. 0 to 90 moles, especially when Z2 is an aromatic diacid, it is preferably 3 Å or less from the viewpoint of i-line permeability when the resin is formed. In the case of the synthetic resin (a), the dicarboxylic acid used in the synthesis of the resin (a) may be used in the presence of helium in the form of a sulphur gas. Dicarboxylic acid and excess amount of sulfoxide in the presence of a catalyst such as N-dimethylformamide, pyridine or vaporized benzyltriethylamine The reaction is carried out, and the excess sulfite gas is heated and depressurized, and the method of distilling off can be obtained by recrystallizing the residue of the reaction liquid with a solvent such as hexane or toluene. In the unpurified state, it is used for the polymerization of the resin. Alternatively, the following catalyst may be used, that is, a dehydration condensing agent such as dicyclohexylcarbodiimide may be used to dicarboxylic acid and N-hydroxybenzotriazole (hereinafter also Known as "HOBT") is a catalyst for the formation of HOBT active esters. As a cockroach! The structure and the phenolic hydroxyl diamine can be preferably used: 2,2-bis(3-amino-4-phenylphenyl)propane, 2,2-bis(4-amino-3-men Phenyl)propane, 3,5-diamino-1-pyridylbenzene, 4,6-diamino-i,3-di-diphenyl, 3,3'-dihydroxy-4,4' -diaminobiphenyl, 4,4'-dihydroxy-3,3,-diaminobiphenyl, 3,4-dihydroxy-3',4'-diaminobiphenyl, bis(3-amine 4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl) sulfide, bis(3-amino-4-hydroxy 136993.doc -31- 200940601 phenyl) form, double (4-Amino-3-hydroxyphenyl)methane, bis(4-amino-3-phenylphenyl) hard, and the following compound group: [Chem. 37]

〇 ❹ The above diamines may be used singly or in combination of two or more. Further, 2'2-bis(3-amino-4-hydroxyphenyl) is preferred in terms of a high light sensitivity when the resin composition is formed and a higher film thickness at the time of development. Acetylene and bis(4-amino-3-ylhydroxyphenyl)indole, and the following compound groups: 136993.doc •32· 200940601 [Chem. 38]

In addition to the higher light sensitivity when the resin composition is formed and the higher film thickness at the time of development, the mechanical elongation of the film after heat curing is higher, and further preferably 2, 2-bis(3-amino-4-hydroxyphenyl)propane. In addition to the higher sensitivity of the film and the higher film thickness at the time of development, it is preferred that the undulating pattern after heat curing has a higher chemical resistance to the organic solvent. The following group of compounds: 136993.doc •33- 200940601 [化39] i §

❹ In addition to the higher sensitivity of the light sensitivity, the adhesion of the film after heat hardening to the sealing resin = the use of a pre-baked film by a pre-baked film in the semiconductor manufacturing step It is preferable that the following compounds are fresh: 1. In terms of labor, I36993.doc -34, 200940601 [40]

In the case of using bis(4-amino-3-hydroxyphenyl) ruthenium, it is preferable to consider the phenolic hydroxy ◎ It acidity. It is preferred to copolymerize the diamine without the desired trans group, or to use a larger molecular weight. The dicarboxylic acid is adjusted to the concentration of the phenolic hydroxyl group. The concentration of the divalent base group in the 1 g of the bis (4-amino-3)-based phenyl group is preferably 2.0 to 5. 〇 millimol, and further preferably 25 ~4·5 millimoles' the best is 3.0~4.0 millimoles. The diamine having a structure and a phenolic hydroxyl group may also be the same as the above-mentioned diamine having a & structure and a phenolic hydroxyl group. When the resin (4) of the present invention is produced, in addition to the above-mentioned diamine, a diamine (hereinafter referred to as "non-phenolic diamine") which does not contain a phenolic hydroxyl group may be copolymerized as needed, thereby controlling the checkability. Solubility and physical properties of aqueous solutions. The non-promising diamine is an organic group having 2 to 4 valences of a tooth atom, and among them, an aromatic diamine having a carbon number of 6 to 30 which does not contain a desired transradical group, and a diamine polyalkane are preferred. . Specifically, hydrazine (or 3,41_, 3 3, _, 24·_) diamino strepyl ether, 4,4, (or 3,3,-) diaminodiphenyl hard, 44, ( Or 33·-) diaminodiphenyl sulphide, 4,4,-benzophenone diamine, 3,31-dibenzoylamine diamine, 4, 仏136993.doc •35· 200940601 one (4 -aminophenoxy)phenylhydrazine, 441_bis(3aminophenoxy)phenyl milling, 4,4-bis(4-aminophenoxy)biphenyl, anthracene, 4_bis (4 _Aminophenoxy)benzene, 1,3·bis(4-aminophenoxy)benzene, 2,2_bis{4_(4-aminophenoxy)phenyl}propane, 3,3| ,5,5,-tetramethyl-4,4,-diaminodiphenylmethane, 2,2|•bis(4·aminophenyl)propane, 2,2,6,6,-four Methyl 4,4,-diaminobiphenyl, 2,2·,6,6,-tetrakis(trifluoromethyl)-4,4,diaminobiphenyl, bis{(4-aminobenzene) Base) _ 2-propyl} 1'4-benzene, 9, bis (cardylaminophenyl) fluorene, bismuth (4 amino phenyloxyphenyl), 3,3, dimethyl Aniline, 3,3,-dimethoxybenzidine, aromatic diamine such as 3,5-diaminobenzoic acid; 2,6-diaminopyridine, 2, aryldiamine-based, double ( 4·amine basic Diamines such as the base 2_propyl)_ι, 4_benzene, and diaminopolyxoxane compounds "The non-phenolic diamines may be used singly or in combination of two or more. In order to actually synthesize the resin (a) of the present invention, a phenolic diamine or a non-phenolic diamine may be dissolved in a suitable solvent such as N-methylpyrrolidone or N,N_:methylacetamide, and pyridine may be added. A tertiary amine such as triethylamine is used as a catalyst, and the compound obtained by vaporizing the above-mentioned di-g-carboxylic acid ruthenium is dissolved in a suitable solvent such as r-butyrolactone or acetone, and added dropwise to _3 (rc) In the solution of the above phenolic diamine or non-phenolic diamine, the target polycondensation structure is obtained. With respect to the resin (a) of the present invention, only the above polybenzoxazole precursor unit can be used. The polyimine unit may also be copolymerized as needed. The polyimine unit has a phenolic hydroxyl group obtained by cyclizing and condensing a tetracarboxylic dianhydride with an aromatic diamine having a phenolic hydroxyl group. In the case of a polyvalent imine unit containing a phenolic hydroxyl group, it is preferred that Z3 is a tetravalent organic group which does not contain a halogen atom, and particularly preferably 136993.doc -36 - 200940601 has a carbon number of 8 a compound of aromatic tetracarboxylic dianhydride of ～36 and an alicyclic tetracarboxylic dianhydride having a carbon number of 6 to 34. Specific examples thereof include 5- (2,5-dioxotetrahydro | furyl)-3_methyl-cyclohexene dicarboxylic anhydride, pyromellitic dianhydride, 1'2,3,4-benzenetetracarboxylic dianhydride, 3, 3,4,4,_dibenzophenone tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethyl-|tetradecanoic dianhydride, 3,3,,4,4,_biphenyl Tetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4,4-diphthalic dianhydride, 1,1-ethylene-4,4 ,-diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, l52_extended ethyl-4,4,_diphthalic acid 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 15-pentamethylene _ 4,4,_diphthalic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, thio- 4,4'-di-o-dicarboxylic acid dianhydride, sulfonyl _4, 4,-diphthalic dianhydride, iota, bis(3,4-dicyclopentyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride 1,4_bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1>3 bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1 ,4-bis[2-(3,4-dicarboxyphenyl)-2-propane ]] dianhydride, bis[3·(3,4-dicarboxyphenoxy)phenyl]decane 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 Dihydride, bis(3,4-dicarboxyphenoxy)didecyldecane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyl a siloxane dianhydride, 2,3,6,7·naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3, 4,9,10-perylene tetraphthalic acid dianhydride, 2,3,6,7-decanetetracarboxylic dianhydride, 1,2,7,8-phenanthrenecarboxylic acid dianhydride, ethyltetradecanoic acid Dihydride, 1,2,3,4·butane tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentane tetra 136993.doc -37- 200940601 carboxylic acid II Anhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride, 3,3',4,4·-bicyclohexanetetracarboxylic acid dihepatic, several groups·4 , 4,_bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4,-bis(cyclohexane 4,2.:carboxylic acid) dianhydride, 1,2- Ethyl-4,4'-bis(cyclohexanedicarboxylic acid) dianhydride 1,1-Ethylene-4,4'-bis(cyclohexan-1,2-diacid) di-hepatic, 2,2-propylene-4,4'-bis(cyclohexane-1 ,2-dicarboxylic acid)dianhydride,oxy-4,4,_bis(cyclohexyl-1,dicarboxylic acid) dianhydride, thio-4,4·-bis(cyclohexane_丨,2-dicarboxylic acid) Erxuan, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-decene -2,3,5,6-tetradecanoic acid dianhydride, rel-[lS,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6- Spiro-3'-(tetrahydrofuran-2,5,-dione), 4-(2,5-dioxotetrahydron-v-but-3-yl)-1,2,3,4-tetrahydronaphthalene -1,2-di-rebel liver, ethylene glycol _ bis-(3,4-dicarboxylic anhydride phenyl) ether, etc.; among them, 5_(2,5-dioxotetrahydro-3-0 is preferred喊基)-3-Methyl-cyclohexene-1,2-dioxalic anhydride, bis(3,4-di-phenylene) mystery, bis(3,4-dicarboxyphenyl) Di-hepatic, 4,4,-(4,4^ isopropylidene diphenoxy) bis(phthalic anhydride); from the viewpoint of transparency to the enthalpy of mercury lamps, dissolution of alkaline aqueous solution In terms of sex and light sensitivity, among them, 5-(2,5-dioxo) is further preferred. Tetrahydro-3-furanyl) methyl-3 · · · cyclohexene-1,2-dicarboxylic anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride. The diamine having a phenolic hydroxyl group represented by χ3 used in the synthesis of a phenolic hydroxyl group-containing quinone imine unit is selected from the above phenolic diamines (when m3=2) or non-phenolic diamines (m3=〇) Or, 2,4-diaminophenol (when m3 = i, the light sensitivity when p is made into a resin composition, wherein 疋2,2-bis(3-amine) is preferred The condensed water condensation reaction in the synthesis of a quinone imine unit containing a phenolic hydroxyl group can be carried out by the following method: in the presence of an acid or a catalyst. Under the conditions, the above tetradecanoic dianhydride and the above diamine are heated to 30t~22 (rc, preferably heated to ~20 (rc. As an acid catalyst, it can be used when making the brewed imine) An organic acid such as sulfuric acid or an organic acid such as p-toluene may be used. γ-Pentyl vinegar and (4) may also be used. As the base catalyst, acridine, diethylamine or dif-amino group may be used. Specific bite, i, 8_ two gas heterobicyclic ring (5, 4, ninety-one -7, U3A7-tetraazatricyclo („, 】 mountain 3, 7) 癸, triethylenediamine, etc. 〇 Further 'can also be used as Method: in particular, in a state in which a polycondensation catalyst or the like is not added, the temperature of the reaction liquid is maintained at a temperature higher than the temperature at which the amidation reaction is carried out, and the water generated by the dehydration reaction is removed by using a solvent azeotropy or the like with water. 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, it is preferred to use a solvent for dissolving the resin in addition to the solvent for the water co-prep. Organic solvent of polarity • As such a polar solvent, butyrolactone, N-decyl pyrrolidone, dimethylformamide, dimethylacetamide, tetramethylurea, cyclobutylate or the like can be used. In the production of the polyimine unit, in addition to the above phenolic diamine, the non-phenolic diamine may be copolymerized as needed to control the solubility and physical properties of the alkaline aqueous solution. In the case of tetracarboxylic dianhydride or two or more kinds of phenolic diamines or non-phenolic diamines, a block copolymer condensate obtained by successive reaction can be obtained; when three or more components are added, At the same time to the opposite 136993 .doc _39· 200940601 The raw material is added to make a random copolymer condensate. The disc resin (4)' can copolymerize the above polyphenylene and sit on the precursor unit and the polyimine unit. The saponin light sensitivity polymerization ratio can be arbitrarily Choice, in terms of brewing ==, 'preferably polyphenylene and ten sitting precursor units: the ratio of quinone imine is 10·· 90~100: range of 。. S tree & (a) The end can be modified by the terminal group. As a method of repairing the end, when adding the resin, the appropriate amount is added as follows: butylene phthalic anhydride, butyl ruthenium ruthenium ruthenium succinic anhydride, cinnamic anhydride, 5 _ drop Acetic anhydride, 4_ alkynyl phthalic anhydride, phenyl ethynyl phthalic anhydride, 3,6-epoxy...fine hydrogen phthalic acid, 4_cyclohexene decantate Cyclohexane-1,2-dicarboxylic anhydride, 4·methylcyclohexane-1,2-dicarboxylic anhydride, 4-aminostyrene, 4·ethynylamine, 3-ethynylaniline, and the like. Among them, in order to increase the mechanical elongation or to increase the glass transition temperature, it is preferred to add at least the old terminal group selected from the group consisting of the following structures: [Chem. 41]

0 HOOC"^^. Further, the dicarboxylic acid used in the present invention may be left as a terminal. With respect to the weight average molecular weight of the resin (a), it is preferred that the weight average molecular weight in terms of polystyrene is 3, _~100,000, and the amount of * is 136,993.doc -40 - 200940601 when the mechanical properties are further increased. Helmet 7Λλλλ, when the slave is below 70,000, at 2.38. /〇 The dispersibility in the hydrazine aqueous solution is improved. ❹

Regarding the resin solution produced, 'the resin (4) can be isolated by a purification step to dissolve it again in the organic (4), and I is used as a specific purification step, comprising the steps of: firstly, adding to the resin solution obtained by the above-mentioned preparation method A poor solvent such as formazan, ethanol, isopropanol or water causes the resin to precipitate. Then, it is dissolved again in a good solvent such as γ-butyrolactone/methylpyrrolidone, and the solution is passed through a column packed with an ion exchange resin, thereby removing ionic impurities. (4) The dissolved droplets of fhai were added to pure water, and the precipitates were separated by filtration and then vacuum dried. Thereby, it is also possible to remove low molecular weight components or ionic impurities. <Positive Photosensitive Resin Composition> (A) Alkali-Soluble Resin In order to obtain a positive-type photosensitive resin composition, (A) the test-soluble resin containing the resin (a) of the present invention is an essential component β as a resin ( The test-soluble resin other than a) is, for example, a resin having at least one group selected from the group consisting of a phenolic hydroxyl group and a carboxyl group, a resin soluble in an aqueous alkaline solution, or a precursor thereof, and specific examples thereof include a phenol aldehyde. a phenol resin and a derivative thereof, a phenol resin and a resole resin thereof, and a polyhydroxystyrene and a derivative thereof, and a resin having a structure in which the resin is copolymerized in a molecule, the resin of the present invention ( The PBO precursor other than a) is an alkaline aqueous solution soluble polymer, a polyhydrazinium soluble in an alkaline aqueous solution containing a phenolic hydroxyl group, derived from a tetracarboxylic acid and a diamine, and having a carboxyl group in the ortho position of the indole bond. Polyimine precursor. 136993.doc •41- 200940601 In the (4) gel-soluble resin, in order to exert the desired effect, the ratio of the resin (4) (4) of the resin of the present invention is preferably _ 〇 / 〇 or more. 2 〇 quality. Further, it is preferably 40% by mass or more, and most preferably 60% by mass or more. The upper limit is preferably 100 mass/0 0 (B). The photosensitive diazonaphthoquinone compound is used in the case of producing a positive photosensitive resin composition (hereinafter also referred to as "the present composition"). The photosensitive diazonaphthoquinone compound is as follows: a gas-based group of 4 - sulfonic acid vinegar selected from a poly(tetra) compound having a specific structure, and a 12-naphthoquinonediazide group of the polyhydroxy compound. At least one compound of the group consisting of sulfonic acid vinegar (hereinafter also referred to as "NQD compound of a poly-based compound"). The NQD compound of the polyhydroxy compound can be obtained by the following method: according to a conventional method, using a gas-renewed acid or a sulfite gas, the naphthalene-stacked acid compound is made into a sulfonium gas, and the obtained naphthoquinone is obtained. The azide sulfonium gas is subjected to a condensation reaction with the polyhydroxylated σ. For example, it is obtained by subjecting a specific amount of a polyhydroxy compound to 1,2, naphthoquinonediazide in a solvent such as a dioxane, acetone or tetrahydrofuran in the presence of a base catalyst such as triethylamine. The base product is reacted and esterified with 1,5-anthracene gas or 1,2.naphthoquinonediazide-4-4 sulfonium gas, and the obtained product is washed with water and dried. The following 'is a photosensitive diazo naphthalene compound which is obtained by combining with the resin of the present invention to obtain a favorable undulating pattern having high sensitivity and no swelling phenomenon. An nqd compound of a polyhydroxy compound represented by the following formula (Β1): 136993.doc -42· 200940601 [Chem. 42]

Wherein 'k, 卜m, and η each independently represent 1 or 2, and the cores ~!^ are independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a propyl group, and a fluorenyl group. The groups in the group formed by ΥπΥ3 independently represent the free single bond, -0-, -S-, -so-, -S02, -CO-, _c〇2, cyclopentylene, cyclohexylene, a group in which a phenyl group and an organic group represented by the following chemical formula are grouped: [Chem. 43]

(wherein, the ruler ^ and !^2 each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an olefin group, an allyl group, and a substituted allyl group); 44] (CH2)

R! 6 13 —-c—

Rl4 and w represent (wherein R"~R16 independently represent a hydrogen atom or an integer of alkyl 1~5); and 136993.doc -43· 200940601 [Chem. 45]

(wherein R17 to R20 each independently represent a hydrogen atom or an alkyl group)}. The NQD compound of the polyhydroxy compound described in [Chem. 18] to [Chem. 32] of JP-A-2001-109149 is exemplified as a specific compound. Among them, in terms of the sensitivity of the positive photosensitive resin composition, the NQD of the following polyhydroxy compound is preferred: [Chem. 46]

2. An NQD compound of a polyhydroxy compound represented by the following formula (B2): [Chem. 47]

(B2) wherein Z represents at least one tetravalent group selected from the group consisting of the following formula: 136993.doc -44- 200940601 [Chem. 48]

R21 ' R22 ' R or 1, a, c, d and i are respectively independent of the above table}. 23, and Han 24 respectively represent the organic group of valence, b denotes 〇, and e respectively represent an integer of 〇~3, an integer of f, g, 匕, 〇 22, where f, g, h, and 丨The total amount is Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο 化合物 化合物 化合物 化合物 化合物 化合物 化合物 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. Among them, in terms of high sensitivity and low precipitation in the positive photosensitive resin composition, the following NQD compounds of polyhydroxy compounds are preferred: [Chem. 49]

[化 50] ❹

136993.doc -45· 200940601 [化51]

[化52]

3. An NQD compound of a polyhydroxy compound represented by the following formula (B3): [Chem. 53]

(B 3) In the formula, k represents an integer of 3 to 8, and kxj L each independently represents a monovalent organic group having one or more carbon atoms, j represents an integer of 1 to 5, k T, and k S each independently represents a monovalent group selected from the group consisting of a hydrogen atom and a monovalent organic group. As a specific preferred example, those described in [Chem. 24] and [Chem. 25] of JP-A-2004-347902 can be cited. 136993.doc -46- 200940601 Among them, in terms of high sensitivity and low precipitation in the positive photosensitive resin composition, the following polyhydroxy compound is preferred: wherein p represents 0 An integer of ~9}2NQD compound: [Chem. 54]

4. An NQD compound of a polyhydroxy compound represented by the following formula (B4): [Chem. 55]

Wherein A represents an aliphatic divalent organic group containing a tertiary or quaternary carbon, and Μ represents at least one divalent group selected from the group represented by the following chemical formula: [Chem. 56] cf3 Ο 0 II II, -1 -1 C - } ° 0 As a specific compound, those described in [Chem. 22] to [Chem. 28] of JP-A-2003-131368 can be cited. 136993.doc -47- 200940601 Among them, the NQD of the following polyhydroxy compound is preferred in terms of the lower sensitivity of the southerly positive photosensitive resin composition:

[化57]

5. An nqd compound of a polyhydroxy compound represented by the following formula (B5): [Chem. 58]

(B 5) ❹ {wherein, R25 represents an organic group represented by the following formula: [Chem. 59] VIII / (R26)r - CH2 (wherein R26 independently represents an alkyl group and a cycloalkane At least one monovalent organic group, and r is independently an integer of 〇~2, and may be the same or different, and q is independently an integer of 〇2. Specific examples of the compound include nqd 136993.doc-48-200940601 of the poly-based compound described in JP-A No. 2,41,9849. Among them, the NQD of the following polyhydroxy compound is preferred in terms of high sensitivity and low precipitation in the positive photosensitive resin composition: [Chem. 60]

[化 62]

136993.doc -49- 200940601 6. NQD compound of a polyhydroxy compound represented by the following formula (B6): [Chem. 63]

In the formula, R27 represents a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, and a cycloalkyl group}.

Specific examples of the compound include those described in [Chem. 18] to [Chem. 22] of JP-A-2001-356475. Among them, in terms of high sensitivity and low precipitation in the positive photosensitive resin composition, it is preferred that the following NQD of the polyhydroxy compound is: [Chem. 64]

7. An NQD compound of a polyhydroxy compound represented by the following formula (B7): [Chem. 65]

In the formula, a plurality of R28 independently represent a monovalent organic group represented by the following formula: 136993.doc -50- 200940601 [Chem. 66]

(wherein Rw each independently represents an alkyl group or a cycloalkyl group, and t each independently represents an integer of 0 to 2) 's each independently represents an integer of 〇~2, and r29 represents a hydrogen atom, a leukoyl group or a cycloalkyl group} . n As a specific compound, the nqd compound of the polyhydroxy compound described in [Chem. 15] and [Chemical Formula 16] of JP-A-2005-008626 is exemplified. Among them, in terms of high sensitivity and low precipitation in the positive photosensitive resin composition, the following NQD compounds of polyhydroxy compounds are preferred: [Chem. 67].

[68]

'The photosensitive resin is combined with the same development time to form a pattern in the above-mentioned photosensitive diazonaphthoquinone compound, which has high sensitivity. With the same exposure amount and phase 136993.doc 51 200940601, the film thickness is wide and precipitates. The lower aspect is the NQD of the following polyhydroxy compound:

CH3—C—CH3 Ο ❹

OH In the present composition, 'as a photosensitive diazona boiled compound, the arsenic can be used as a good base', and the ground can be used as a 5-naphthoquinonediazidesulfonyl group or 4-anthracene. Any of the diazanesulfonyl groups. 4 bribes Λ & Nai Cong test 4_naphthoquinonediazide sulfonate compound in the i-line region of the silver lamp is absorbent 'suitable for sputum exposure. The absorption of the % naphthoquinone bismuth sulfonate compound is extended to the g-line region of the mercury lamp, and is suitable for g-line exposure in the present invention. It is preferred to select the heart naphthalene stack by performing the wavelength of the exposure. Nitrogen G-supplement compound, azide (tetra) brewing compound. Further, a naphthoquinonediazide sulfonate compound which can be obtained in the same molecule and is made of a naphthoquinone, a 5-naphthoquinonediazidesulfonyl group, or a mixture of 4 naphthalenes. The nitrogen is continuously brewed from the compound and the naphthalene-branched azide can brewing compound. In the group of the present invention, the amount of the photosensitive diazonaphthoquinone compound to be added is from 1 to 100 parts by mass, preferably from 3 to 40 parts by mass, based on 100 parts by mass of the (4) of the test-soluble resin. When the amount of 1 〇 to 3 〇 parts by mass is 1 or more, the sensitivity is improved, and when the amount is (10) 136,993.doc -52 · 200940601 or less, the residue after exposure is not generated. (c) Organic solvents ❹

Examples of the organic solvent used in the case of producing a resin composition using the resin of the present invention include N-methyl-2-pyrrolidinone, N,N-methylethylamine, and N as a polar solvent. N-dimethylformamide, dimethyl sulphate tetramethylurea γ-butyrolactone, morphine, and the like. Further, in addition to the polar solvent, a ketone, a self-acting type, an internal vinegar, an ether, a hydrocarbon, or a hydrocarbon may be mixed as an organic solvent, and for example, acetone or mercaptoethyl may also be used. Ketone, methyl isobutyl hydrazine, cyclohexyl ketone, decyl acetate, acetic acid ethyl succinic acid butyl vinegar, oxalic acid diethyl vinegar, lactic acid ethyl acetate, lactic acid methyl vinegar, (10) butyl ketone, propanol monomethyl ether acetate Ester, propylene glycol monomethyl mystery, benzyl alcohol, phenylethylene glycol, ethylene glycol dimethyl sulfonate, diethylene glycol dimethyl _, tetrahydron-l read, dioxane, 1,2, di-ethane "4-dioxane, gas stupid, ortho-benzene, benzopyrene, hexane, gypsum, benzene, toluene, xylene, mesitylene, etc.: in these, the most It is good that r_butane vinegar: in the case of making a photosensitive resin composition, the in-plane bismuth property of the pre-baked film is more sensitive than that of the two*s: _ exposure amount, same development time to form a pattern: ^The film thickness margin is wider, and the photosensitization rate of the photosensitive diazonaphthalene (tetra) compound is evaluated.) -f is more 焉 (by the viscosity of the composition: in the composition, added (c The amount of the organic solvent to be added, phase / 100 mass & (4) the solubility of the resin, preferably (10) ~ two 'by changing the amount of organic solvent added to control the viscosity. What is better is the quality of the injury' It is preferably in the range of 15 G to 5 (10) parts by mass. When the amount is 136,993.doc -53 - 200940601 100 parts by mass or more, the viscosity of the resin composition is lowered, and the film thickness uniformity of the cloth film is improved. From the viewpoint of the viscosity of the composition, it is preferably 2000 parts by mass or less, and it is usually easy to apply a film thickness of a desired pattern. (D) The alkoxydecane compound is also visible in the resin composition of the present invention. It is necessary to add a secondary auxiliary agent for improving the adhesion to the substrate. Examples of such a secondary auxiliary agent include alkyl imidazoline, butyric acid, polyhydroxystyrene, polyvinyl decyl ether, and third butyl phenol aldehyde. A varnish, an epoxy decane, an epoxy polymer, a tris-propyl propyl triethoxy pulverization, and various alkoxy pulverization compounds. Specific preferred examples of the oxyalkylating compound are exemplified by 3- Methyl propylene oxide oxypropyl trialkoxy Burning, 3-methacryloxypropyl dialkoxyalkyl decane, 3-glycidoxypropyl trialkoxy decane, 3-glycidoxypropyl dialkoxypyrene a reaction of 3-aminopropyltrioxoacetate or 3-aminopropyldimethoxyalkyl decane with an acid anhydride or an acid dianhydride; 3-aminopropyldimethoxylate Or the amino group of 3-aminopropyl bis-oxyalkyl ketone is changed to a urethane group or a ureido group. "As an alkyl group at this time, a methyl group, an ethyl group, and a butyl group can be cited. Examples of the acid liver include: cis-succinic anhydride, phthalic anhydride, etc.; as the acid dianhydride, pyromellitic dianhydride, 3,3', 4,4'-diphenyl Ketone tetradecanoic acid dianhydride, 4,4,-oxydiphthalic acid monohepatic, etc.; as the urethane group, a third butoxy group amino group, etc.; Examples include a strepylaminocarbonylamino group and the like. As a preferred alkoxydecane compound, the following alkoxydecane compound is preferable in terms of the following: 136993.doc • 54· 200940601 When the shape is developed The pattern is well adhered to the substrate, and the adhesion to the substrate after heat curing is high, and the reactivity of the photosensitive agent such as the photosensitive diazonaphthoquinone compound in the photosensitive resin composition is low, and the composition is low. The stability over time is high: [Chem. 70]

i? SV HO—C—Xj-C—N—X2—Si—(O—X4)3-s (18) where X1&X2 represents a divalent organic group, and X3 and X4 represent a monovalent organic group. And s represents an integer of 〇~2}; [71] (Xs)s Η Ο

(X6-0)3-s_Si_X7~N—C, x,c〇〇H HOOC^ (O—Xn)3-s (19) 〇Η (Χ,ο), {where, X7 and X9 indicate 2 valence The organic group, X8 represents a tetravalent organic group, X5, Χ6, Χίο, and χπ represent a monovalent organic group, and s represents an integer of 〇~2};

[化72]

Qi\2)fX~ XI3—Si—(O—X15)3.s ^ |xh)s (2〇) {wherein, Xi3 represents a divalent organic group, and X12, 乂14 and 乂15 represent a monovalent organic group. , s represents an integer of 0 to 2, and t represents an integer of 0 to 5}; [化73] Ο Η χ16-C-N-Xj7-Si-(OX19>3-s (2 1> (Xl8)s 136993 .doc -55- 200940601 {wherein, Xl6 represents -NH-R20 or -〇-Κ·21 (Κ·20 and Κ·21 is a monovalent organic group containing no COOH group); χ17 represents a divalent organic group' Xi8 and Χι9 represent a monovalent organic group, and s represents an integer of 〇~2}; [Chem. 74]

HS—X22—Si—(OX24>3-S (X23)S (2 2) {wherein, X22 represents a divalent organic group 'X23 and X24 represents a monovalent organic group' and s represents an integer of 0 to 2}; © [Chem. 75] (2 3) H2N—C—NH—X25~ Si—(0X27)3-5 0 (X26)s {wherein, Xu represents a divalent organic group, and Xu and Xu represent a monovalent organic group. And s represents an integer of 0~2}; [Chem. 76] ❹ ((X28)2N) u-

X29—X3〇—Si—(0X32)3.: (X3l)s (2 4) X29 is selected from the valence of the lower genus group. In the formula, Xu represents a hydrogen atom or a methyl group: [Chem. 77]

"ch2--S〇2——一 O—C—NH ο ο II NH-C-NH--C 〇O II II ——C—O—*—O—C— 0 II C—NH— oo ...II I) CF3 O -C— —NH—ί!— cf3 136993.doc -56- 200940601 , Xm represents a divalent organic group, and “and 32 represents an organic group of valence, and s represents an integer of 〇~2, And u represents an integer of 1 to 3}; and [化78] \_7^~X33~X34—Si—(OX36)3-S (X35)s (2 5) {wherein, X33 and X34 represent a divalent organic The base, X35 and X36 represent an i-valent organic group, and s represents an integer of 0 to 2}. 〇❹ The addition amount in the case of adding a secondary auxiliary agent, relative to the mass fraction of (A) alkali-soluble resin, It is preferably in the range of 1 to 2 parts by mass of 〇〇. (E) a compound which causes a crosslinking reaction by heat in the resin composition of the present invention, in order to increase the glass transition temperature of the film after heat curing, or The solvent resistance to various organic solvents is increased, and a compound which causes a crosslinking reaction by heat (hereinafter also referred to as a thermal crosslinking agent) may be added as needed. Here, as a temperature at which a crosslinking reaction is caused, it is preferred that 150 3 50 C. Cross-linking reaction is borrowed i is a specific component when it is developed to form a pattern and then subjected to heat treatment, and is preferably selected from compounds having an epoxy group, a fluorenylmethyl group, an alkoxymethyl group, or an oxetanyl group, and a diene. The propyl bis-imine compound is at least one compound in the group. As the compound having an epoxy group, specifically, a bisphenol A type epoxy resin, a double hop F type epoxy resin, a double epoxide type epoxy resin Tree gambling, A (four) varnish-type epoxy resin, benzene (four) varnish-type epoxy resin, glycidylamine epoxy resin, polysulfide type epoxy resin. I36993.doc -57- 200940601 as a hydroxymethyl group The compound or the compound having an alkoxymethyl group is specifically s, preferably a compound having two or more monovalent organic groups represented by the formula (A) in the molecule: [Chem. 79] and式) { wherein, El is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms}. 感光 A photosensitive resin composition is prepared from a compound having a methyl group or a compound having an oxymethyl group. From the viewpoint of viscosity stability at the time of storage at room temperature, it is preferred that a compound having an alkoxyfluorenyl group. The compound having a mercapto group or a compound having an alkoxymethyl group is further selected from the group consisting of a compound having a desired trans group, and a compound of the formula (B). a compound containing a divalent organic group: " [80]

(B) e2 {wherein, E2 is a hydrogen atom or an alkyl group having a carbon number of 丨~6, and at least one of the groups consisting of the compound represented by the formula (4)): 136993.doc •58 · 200940601 [化81]

E3—OH; E3—OHzCs. E Factory OH2C

(C) wherein, E3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the compound having a phenolic hydroxyl group include the following compounds:

H3c ch3

Ch2ch3

136993.doc -59- 200940601 [Chem. 83]

The compound containing a divalent organic group represented by the formula (Β) includes the following compounds: [Chem. 84] Ο 1? l H3COH2, N/\N/CH2〇CH3 H3COH2C-NH-C-NH-CH2OCH3 If H3CH2COH2C-NH-C-nh-ch2och2ch3 ΛΛ H3CH20 OCH2CH3 9 H Na丄C(4) HjCHzCOHr^^N <CH2OCH2CH3 )~~( NNW H3CH20 OCH2CH3 A JSL ff H3COH2cT 丫CH2〇CH3 h3ch2coh2cx J\ -,ch2och2ch3 0 ,NN Mn H3CH2COH2C Y vch2och3ch3 0 ; These may be used singly or in combination of plural kinds. The oxime 2 of the formula (Β) is a monovalent organic group, preferably an alkyl group having a carbon number of 1 to 20, and a resin composition. More preferably, it is an alkyl group having a carbon number of 1 to 10, and most preferably an alkyl group having a carbon number of 1 to 4. As a divalent organic compound represented by the general formula (C) The compound of the base may, for example, be 136993.doc -60- 200940601 The following compound: [Chem. 85] H3COH2C, n, CH2〇CH3 h^coh2c^ f h3coh2c

A ch2och3 ch2och3 The E3 group of the formula (C) is a monovalent organic group, preferably an alkyl group having a carbon number of from 丨 to 2〇, and more preferably a carbon number in terms of solubility of the resin composition. The oxime is an alkyl group of 1 to 10, and most preferably an alkyl group having 1 to 4 carbon atoms. The compound having an oxetanyl group is specifically a compound having one or more 4-membered cyclic ether structures in one molecule, and can be subjected to cationic ring-opening polymerization or carboxylic acid, thiol or phenol. Addition reaction. For example, 1,4-bis{[(3-ethyl_3_oxetanyl) methoxyl]methyl}benzene, bis[1-ethyl(3-oxetanyl)] Methyl ether, 4,4,_bis[(3_ethyl_3 oxetanyl)methoxymethyl]biphenyl, 4,4,-bis(3-ethyl-3-oxetanyl) Oxyfluorenyl)biphenyl, ethylene glycol bis(3_ethyl_3_oxetanylmethyl)ether, diethylene glycol bis(3-ethyl-3.oxetanyl)ether, Bis(3_ethyl_3_oxetanylmethyl)diphosphate, trimethylolpropane tris(3-ethyl-3-cyclohexanylmethyl), pentaerythritol tetrakis(3-ethyl_3· Oxetheylmethyl) mystery, poly[[3·[(3·ethyl·3_oxetanyl)methoxy]propyl] sesquiterpene] derivatives, oxetane oxime An ester, a phenol novolac type oxetane, a bis-bis((3-ethyloxetan-3-yl)methoxy)benzene, etc., but is not limited thereto. These may be used singly or in combination of plural kinds. Examples of the bisallyldiimide compound include the following compounds 136993.doc -61- 200940601: [Chem. 86]

The blending amount in the case of the component containing the hot cross-linking agent can be based on the cross-linking effect, the deformation of the pattern in the heat treatment after development, and the allowable range of the residue generated during development. The amount of the most suitable addition is selected in combination with respect to 1 part by mass of the (4) volume-sensitive resin, preferably 0.5 to 50 parts by mass, more preferably Μ by mass: (F) selected from the group consisting of acrylic vinegar compounds a compound of the methacrylic acid lysate compound, a methoxy group-containing compound, or at least one compound of the group, which is composed of the compound of the present invention, may contain the above compound (F) in relation to The type and molecular weight of the polymer are varied to determine the dissolution rate, and the display can be carried out in a precise development time range. 136993.doc • 62· 200940601 The acrylate compound and the methacrylate compound are selected from the group consisting of acrylates and oximes. A compound of the group consisting of acrylates, acrylamides, and methacrylamides. Specific examples of the preferred ones include: NK-ESTER series M-20G, M-40G, M-90G, M-230G, CB-1, SA, S, AMP-10G manufactured by Shin-Nakamura Chemical Industry Co., Ltd. AMP-20G, AMP-60G, AM-90G, A-SA, LA, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, HD, NPG, 9PG, 701, BPE-100, BPE-200, BPE-500, BPE-1300, A-200, A-400, A-600, ❹ A-HD ' A-NPG ' APG-200 ' APG-400 ' APG-700 ' A-BPE-4, 701A, TMPT , A-TMPT, A-TMM-3, A-TMM-3L, A-TMMT, and LIGHT ESTER series manufactured by Kyoeisha Chemical Co., Ltd., E, NB, IB, EH, ID, L, L-5, L-7, TD, L-8, S, MC, 130MA ' 041MA 'CH, THF, BZ, PO, IB-X, HO, HOP, HOA, HOP-A, HOB, A, HO- MS, HO-HH, HO-MPP, G, P-1M, P-2M, EG, 2EG, 1.4BG, 1.6HX, o 1.9ND, TMP, G-101P, G-201P, BP-2EM, TB, IS, MTG, BO, CL, 3EG, 4EG, 9EG, MEG, NP, M-3F, M_4F, M-6F, FM-108, 1.3BG, 1.10DC. Further, LIGHT ACRYLATE series IAA, LA, SA, BO-A, EC-A, MTG-A, 130A, DPM-A, PO-A, P-200A, NP_4EA, NP manufactured by Kyoeisha Chemical Co., Ltd. can be cited. -8EA, THF-A, IB-XA, HOA, HOP-A, M-600A, HOA-MS, HOA-MPE, 3EG-A, 4EG-A, 9EG-A, 14EG_A, NP-A, 136993.doc 63- 200940601 1.6HX-A, 1.9ND-A, DCP-A, BP-4EA, BP-4PA, TMP-A, TMP-6EO-3A, PE-3A, PE-4A, DPE-6A, BA-104 , BA-134, G-201P. In addition, EPOXY ESTER series M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M, and 3002A manufactured by Kyoeisha Chemical Co., Ltd. can be cited. Also, ARONIX series PCT-101, M- manufactured by Toagosei Co., Ltd. 102, M-110, M-lll, M-113, M-117, M-120, ❹ Μ-208, Μ-210, Μ-211, Μ·215, Μ-220, Μ-225, Μ-233 ,Μ-240,Μ-245,Μ-260,Μ-270,Μ-305,Μ-309, Μ-310, Μ-315, Μ-320, Μ_350, Μ-360, Μ-400, Μ-408 Μ-450, Μ-5300, Μ-5400, Μ-5600, Μ-5700 ° Further, DMAEA, DMAPAA, DMAA, ACMO, ΝΙΡΑΜ, and DEAA manufactured by Xingren Company can be cited. These compounds may be used singly or in combination of two or more kinds thereof. Examples thereof include allyl-containing compounds, and examples thereof include allyl alcohol, allylanisole, allyl benzoate, and allyl cinnamate. Ν-allyloxyphthalimide, allyl phenol, allyl phenyl sulfone, allyl urea, diallyl phthalate, diallyl isophthalate, Diallyl terephthalate, diallyl maleate, diallyl isocyanurate, triallylamine, triallyl cyanurate, cyanuric acid Allyl ester, triallylamine, triallyl 1,3,5-benzenetricarboxylate, triallyl trimellitate (TRIAM7〇5 manufactured by Wako Pure Chemical Industries, Ltd.), pyromellitic acid III Allyl ester (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.), Oxygen phthalate 136993.doc •64· 200940601 Diallyl monoacrylate, triallyl phosphate, triallyl phosphite, diallyl citrate ester. These compounds may be used singly or in combination. As the methoxy group-containing compound, the following compounds can be mentioned: [Chem. 87] 〇

Och3

Ch3o

Och3 ch3〇—^ y_ c_ch2-c—〇ch3 As the phenyl ester compound, the following compounds can be cited: [Chem. 88]

The blending amount in the case of dissolving the above-mentioned dissolution inhibitors is preferably from 1 to 20 parts by mass, based on 1 part by mass of the (A) dry-soluble resin. If the amount of the inhibitor is less than i., the weight of the shellfish will not obtain sufficient dissolution inhibition effect; on the contrary, if it exceeds 50 mass, 136993.doc -65- 200940601, the dissolution inhibitor will evaporate during thermal hardening. The air dispersion and the residual film rate are lowered, so that the thickness of the cured film of the target cannot be ensured. () An organic compound having a carboxyl group in the knives (hereinafter also referred to as an acid compound) ❹ ❹ In order to increase the sensitivity, it may be added to the organic compound having a plurality of groups in the molecule, and t is preferably a carbon atom. The 4 to 20 tarenic acid compound 'better has a direct bond structure, a branched chain or a cyclic structure, and the organic group has a carbon number of 6 to 12. Specific examples thereof include: sorbic acid, lauric acid, myristic acid, adipic acid, 2·methyl·4·pentenoic acid, " keto-2-pentenoic acid; 2. methyl ampicillin, A Base-n-valeric acid, 3-methyl-n-valeric acid, 4-methyl-n-valeric acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-decanoic acid, isonanoic acid, DL-leucine, 2_heptic acid, 2. octanoic acid, 2_thick acid, 2-decenoic acid, 9-decenoic acid, 2-dodecenoic acid, 10-deca-decanoic acid, 3-cyclohexenecarboxylic acid , 1_cyclohexene_3·formic acid, cyclohexyl carboxylic acid, cyclopentyl acetic acid, cyclohexylethyl:, cyclohexylpropionic acid, 4-cyclohexanebutyric acid, 5-norbornene-2-carboxylic acid, For the big-mouth succinic acid 2,4-hydroxybenzoic acid, 3,5•dihydroxybenzoic acid, o-toluic acid toluic acid, p-toluic acid, o-columic acid, mesogenic acid to anisic acid, water Salicylic acid, 2,4-dihydroxybenzoic acid, 3,5-di-basic formic acid, 3-phenyllactate, 4-p-phenylphenyl lactic acid, 4-aminolated mandelic acid, 3,4-diaminoglycan Acid, 4_ mercapto-3 methoxy mandelic acid, methoxy=_(1.naphthyl)propionic acid, mandelic acid, 2-phenyllactate, acetamidine mandelic acid, α_methoxyphenyl Acetic acid, etc. Among the carboxylic acid compounds, the sensitivity is improved: in the aspect of high adhesion between the pattern and the substrate during development, particularly good indolephthalic acid, α-methoxyphenylacetic acid. The addition amount of (G) carboxylic acid compound 136993.doc -66 - 200940601 is preferably 5 to 20 parts by mass, more preferably 5 to 1 part by mass. When the amount of the carboxylic acid compound is 5 parts by mass or more, the development residue in the exposed portion is reduced, the sensitivity is also improved, and the adhesion to the ruthenium substrate is also good. When the amount is 2 parts by mass or less, the film thickness at the time of curing is reduced, and the stretched elongation of the film after curing is good. (Other additives) In the photosensitive resin composition of the present invention, a dye, a surfactant, and a dissolution promoter may be added as needed.

❹ The above additives are further specifically described as the dye, and examples of the dye include methyl violet, crystal violet, and malachite green. The amount of addition in the case of adding a dye is preferably in the range of 0.01 to 5 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. Further, as the surfactant, a nonionic surfactant comprising a polyglycol such as polypropylene glycol or polyoxyethylene lauryl ether or a derivative thereof; FLU〇RAD (trade name, manufactured by Sumitomo 3); MEGAFAC (product name: Japan, 4 ink chemical industry company), a few product names, manufactured by Yuan Xiaozi A), etc., gas-based surfactants, κρ (4) (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DM (trade name, Company system k) GLANOLC product name, manufactured by Kyoeisha Chemical Co., Ltd.) and other organic stone oxygen, - interface live! The green agent is preferably an organic stone oxide surfactant. The amount of the addition of the surfactant is preferably in the range of GGi to 5f by weight relative to 00 parts by mass of the (4) test-soluble resin. In addition, as a dissolution promoter, it is preferred to have a condensed radical 136993.doc • 67- 200940601, for example, a linear phenol such as bisphenol, MtrisPC or MtetraPC (manufactured by kenah chemical industry company) TrisP-HAP, TrisP-4 TnsP-PA and other non-straight-bonded phenolic compounds (the state chemical industry company ^ 5 n-hexyl stupid phenol, 2 to 5 hydrogen atoms of the phenyl group of diphenylmethane replaced by a compound of the group, wherein 1 to 5 hydrogen atoms of the phenyl group of 3,3-diphenylpropene are substituted with a trans group compound, bis(3-amino-4-phenyl group) and ruthenium, 2- Cyclohexyldicarboxylic anhydride, ruthenium 2 reactant, etc. The addition amount in the case of adding/dissolving the accelerator is preferably 0.5 to 20 parts by mass based on 1 part by mass of the (A) alkali-soluble resin. <Negative photosensitive resin composition> In the (A) alkali-soluble resin of the present invention, the compound which produces an acid by (H) by irradiation with active light can be used, and (1) by acid The negative-type photosensitive resin composition can be produced by cross-linking the sigma, and will be described in detail below. (Η) by irradiation activity A compound which generates an acid by a line, and a compound which generates an acid by irradiation with an active light is a compound which generates an acid by irradiation with an active light, and examples of the compound include the following compounds. Gas methyl group, uniform spray, one (2,4,6-dimethylmethyl)-homo-, 2-phenyl-bis(4,6-trichloroindenyl)_, two-plow, 2-( 3-oxophenyl)-bis(4,6-trimethylmethyl)_memenomorph, 2_(2_phenylphenyl)-bis(4,6-trichloromethyl)-meanstriene, 2- (4-methoxyphenyl)_bis(4,6-trimethylmethyl) are all ploughed, 2_(3_methoxyphenyl)-bis(4,6_trimethyl)-- Plowing, 2-(2-methoxyphenyl)_bis(4,6-trimethylmethyl)_Jingsan 136993.doc -68- 200940601 p well, 2-(4-mercaptopurenyl)- Bis(4,6-trimethylmethyl)_--------, 2-(3-methylnonphenyl) bis (4,6-tris)-------- Mouth phenyl)_bis(4,6-trimethylmethyl)-average three-plow, 2-(4-methoxynaphthyl)-bis(4,6_trimethylmethyl)-all three tillage, 2 -(3-methoxynaphthyl)-bis(4,6-trimethylsulfonyl)_uniform tillage, 2-(2-methoxynaphthyl)- (4,6-trimethylmethyl)_all three sprays, 2_(3,4,5-trimethoxy-anthracenyl)-bis(4,6-trimethylmethyl)_all three whistles: , 2-(4-mercaptothio-alkynylyl)-bis(4,6-trimethylmethyl)_-all, well, 2·(3-methylthio-diphenyl)- Double (4,6·three gas sulfhydryl)·all three tillage, 2_(2_© fluorenyl thiostyryl)-bis (4,6-trimethyl fluorenyl) _ all three, well and so on. Ii) diallyldiphenylphosphonium tetrafluoroborate, diphenylphosphonium tetrafluorophosphate, diphenyl pin tetrafluoroarsenate, diphenylsulfonium trifluoromethanesulfonate, diphenyl錤Trifluoroacetate, diphenylphosphonium p-toluenesulfonate, 4-methoxyphenylphenylphosphonium tetrafluorophosphonate, 4-methoxyphenylphenylphosphonium hexafluorophosphonate, 'A Oxyphenylphenyl sulfonium hexafluoroarsenate, 4-methoxyphenylphenyl fluorene trifluoromethanesulfonic acid 0, 4-methoxyphenylphenyl trifluoroacetate, cardiomethoxybenzene Phenyl phenyl-p-toluene sulphate, bis(4_t-butylphenyl ruthenium sulfonate, bis(4-t-butylphenyl)phosphonium hexafluoroarsenate, double (4_ Tert-butylphenyl) fluorene trifluoromethane acid anhydride, bis(4_t-butylphenyl)iron trigas acetate, bis(4) tert-butylphenyl)phosphonium-p-toluenesulfonate, etc. . Iii) triallyl sulfonium salt monophenylphosphonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, triphenyl sulfonate, triphenylene Tri-gas acetate, triphenyl wire 4 toluene sulfonate, 4-methoxyphenyl diphenyl hydride four gas I36993.doc •69· 200940601 pharcinate, 4- φ « ** oxime base Lithium hexafluorophosphonate, 4-methoxyphenyl, phenyl hexafluoroantimonate, 4-methoxyphenyl diphenyl sulfonate, 4 methoxy phenyl diphenyl铳Trifluoroacetate, 4-methoxyphenyl diphenyl, nickel-p-toluenesulfonate, 4-phenylthiophene diphenyltetrafluoroborate: 4 phenylsexyl diphenyl hexafluorophosphine Acid salt, 4-phenylthienyldiphenylhexahydrate, 4-phenylnonyldiphenyl trifluoromethaneate, 4-phenylthiophene-phenylidene difluoroacetate 4_Phenylthienyldiphenyl-p-toluate or the like. ❾ In these compounds, 'as a tri-gas sulfhydryl group · three tillage, preferably 2-(3-phenylphenyl)-bis(4,6-trimethylmethyl)_ 2_(4_气笨基)·双(4义三气methyl)-all three sprays, 2_(4•methylthienyl)_double (Μ三气methyl)·all three tillage, 2_(4_ Methoxystyryl) bis(4,6-trimethyl)-three-till, 2-(4-methoxytyl)-bis(4 6_trichloroindenyl) are all cultivated in three ways, Preferred examples of the diarylsulfonium salt include diphenylsulfonium trifluoroacetate, diphenylsulfonium trifluoromethanesulfonate, and 4-methoxyphenylphosphonium trifluoromethanesulfonate. 4-methoxyphenylphenylhydrazine trifluoroacetate or the like; as the triaryl salt, preferably triphenylsulfonium sulfonate, triphenylsulfonium trifluoroacetate, 4- Methoxyphenyldiphenylphosphonium methanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-phenylthiophenyldiphenyldifluoromethanesulfonate, 4-phenyl Thienyl diphenyl trifluoroacetate and the like. In addition to the above, the compounds shown below can be used. (1) Diazo ketone compound As the diazonium ketone compound, for example, 1,3-diketone-2-diazide 136993.doc -70. 200940601 compound, diazonium benzoate compound, and example, The phenolic oxime, 夂Cai (2) hard compound diazo naphthalene compound, etc. are listed as specific diazido-4-sulfonate compounds. As a hard compound, for example, the compound and the compound can be a compound of a compound, a brewing--a kind of a nitrogen-containing compound, and as a specific example, it can be classified as a methylene-based, a soft, double (a醯# base sulfonyl) methane and the like. Laughing (this f 醯 ( (3) sulfonic acid compound

As an acid-compounding compound, examples ^^ _p =1 coffee can be enumerated. Burning base acid series, southern ketone sulfonate, aryl sulfonate minus S type, imine acid vinegar, etc. As a preferable specific example, benzoin toluene vinegar, succinct three-in-three (trifluoromethane acid), o-nitrof-trifluoromethane _, o-nitrobenzyl ruthenium Benzene sulfonate and the like. (4) Sulfonimide compound Specific examples of the sulfonimide compound include, for example, N-(trifluoromethylsulfonyloxy)butaneimine and N-(trifluoromethylsulfonyloxy). O-xylyleneimine, N-(trifluoromethylsulfonyloxy)diphenyl cis-butane di-imine, N-(trimethylsulfonyloxy)bicyclo[2 21]g _5_ dilute 2,3. dicarboxy quinone imine, fluorene-(trifluoromethylsulfonyloxy) naphthyl quinone imine, and the like. (5) oxime ester compound 2-[2-(4-mercaptophenylsulfonyloxyimino)]_2,3_dihydrothiophene_3•ylidene]_2_(2-decylphenyl)acetonitrile ( Ciba Specialty Chemicals, Inc., trade name "Irgacure pAG121"), [2_(propyl hydroxy methoxyimino)-2,3-dihydro porphin _3·subunit]_2_(2 Methylphenyl) B 136993.doc 71 200940601 Nitrile (&gt; Feiba Refinery, trade name "Irgacurep AGi〇 3") and the like. (6) Diazomethane-sintering compound Specific examples of the diazo-f-alkane compound include bis(=methylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and (phenyl) Sulfhydryl) diazomethane and the like. In particular, from the viewpoint of sensitivity, the above (5) oxime ester compound is preferred. (H) The addition of a compound which generates an acid by irradiation with active light is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the heat-resistant polymer containing the copolymer of the present invention. When the amount is 5% by mass or more, the amount of the acid generated by the irradiation of the active light is sufficient, and the sensitivity is improved. When the amount is 20 parts by mass or less, the mechanical properties after curing are not lowered. (I) Compound which can be crosslinked by the action of an acid Hereinafter, the compound which can be crosslinked by the action of an acid will be described. When (I) a compound which can be crosslinked by the action of an acid is added, when the coating film is heat-hardened, the (A) alkali-soluble resin may be cross-linked, or the network itself may be formed, thereby strengthening Heat resistance. (I) The compound component which can be crosslinked by the action of an acid is preferably a melamine resin selected from the group consisting of a mercapto group or an alkoxymethyl group and a monomer thereof, and a urea resin and a monomer thereof. . Examples of such an alkoxylated melamine resin, an alkoxymethylated benzene melamine resin, a hospital oxymethylated glycoluril resin, an alkoxymethylated urea resin, and the like Wait for the monomer. Among these, alkoxymethylated melamine resin, alkoxy 136993.doc • 72· 200940601 methylated benzene melamine resin, alkoxymethylated glycol urea resin, alkoxylated urea The resin, and the monomers can be obtained by the following methods: a correspondingly known hydroxylated melamine resin, a hydroxylated phenyl melamine resin, a methylolated urea resin, and a monomer thereof The hydroxymethyl group is changed to an alkoxymethyl group. Examples of the type of the alkoxyfluorenyl group include a methoxyindenyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, and can be preferably used: in practical applications. Sale of SAIMERU 300, 301, 303, 370 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by MITSUI SCITECH Co., Ltd.) , NIKALAC MX-270 '-280 &gt; -290 'NIKALAC MS-11 'NIKALAC MW-30, -100, -300, -390, -750 (made by SANWA CHEMICAL). These compounds may be used singly or in combination. The monomer of the above resin is also used as a crosslinking agent, and examples thereof include hexamethoxy Ο ^ methyl melamine, dimethoxymethyl urea, and the like. The amount of the compound which can be crosslinked by the action of the acid is preferably from 3 to 50 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. When the amount is 3 parts by mass or more, the crosslinking is sufficiently performed, and the patterning property is improved. When the amount is 50 parts by mass or less, the mechanical properties after curing can be maintained. In addition, in the negative photosensitive resin composition, (C) an organic solvent, (D) an auxiliary agent, and (E) may be added to the positive photosensitive resin composition as needed. And the compound causing the crosslinking reaction, 136993.doc -73- 200940601 (other additives). &lt;Method of Forming Curing Rough Pattern&gt; An example of a method of forming a hardened relief pattern on a substrate (hereinafter also referred to as "the present method") using the photosensitive resin composition of the present invention is shown below. First, a coating step of forming the composition on a substrate in the form of a layer or a film is carried out. The substrate is applied, for example, to a tantalum wafer, a ceramic substrate, a substrate, or the like. At this time, in order to improve the adhesion between the formed undulating pattern and the substrate, a bonding aid such as a decane coupling agent may be applied to the substrate in advance. © can be carried out by spin coating using a spinner, spray coating using a sprayer, dipping, printing, roll coating, and the like. Then, pre-baking is performed at 80 to 140 ° C, and after the coating film is dried, the layer or film is chemically lined through a mask using an exposure device such as a contact aligner, a mirror projection exposure machine, or a stepper. Exposure is performed, or an exposure step is performed in which light, electron lines or ion lines are directly irradiated. As the chemical line, X-rays, electron beams, ultraviolet rays, visible rays, or the like can be used, and those having a wave length of 200 to 50 Å are preferable. In terms of the resolution and operability of the pattern, the wavelength of the light source is preferably such that the i-line is more preferably a twisted line. As the exposure means, a contact aligner, a mirror projection exposure machine, and a stepper are particularly preferable. Then, after the exposure was carried out only in the case of the negative photosensitive composition, it was further heated at 80 to 14 CTC for 30 seconds to 600 seconds. This is called post-exposure bake (hereinafter also referred to as PEB (Post Exposure Bake)). By this step, the acid generated by the exposure is used as the catalyst 'exposure portion. (I) The compound which is linked by the action of the acid causes a thermal crosslinking reaction, and is insoluble in the aqueous test solution. 136993.doc -74- 200940601 'In the case of a positive photosensitive composition, a developing step of eluting and removing the exposed portion by a developing solution is performed, and in the case of a negative photosensitive photosensitive composition, dissolution is carried out with a developing solution The developing step of the unexposed portion is removed. The developing method may be selected from a dipping method such as a stirring method or a rotary jet method. As the developer, inorganic tests such as sodium hydroxide, sodium carbonate, sodium citrate, and ammonia water; organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and tetramethylammonium hydroxide can be used. An aqueous solution obtained by adding a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to a quaternary ammonium salt such as tetrabutylammonium hydroxide or the like. Among them, a tetramethylammonium hydroxide aqueous solution having a concentration of 〇 5% to 1% by weight, more preferably from 1.0% to 5%, is preferred. Further, as far as it is generally used in the semiconductor manufacturing step, it is preferably 2.38%. After development, the developing solution is removed by washing with an eluent, whereby an undulating pattern formed on the substrate can be obtained. As the eluent j, water, methanol, ethanol, isopropyl alcohol or the like can be used alone or in combination. Finally, a heating step of heating the undulating pattern of the test resin obtained in the above manner is carried out. The heating temperature is preferably 18 〇 or more. Usually, it is heated to 25 CTC to 40 (TC), and the component having low heat resistance contained in the additive component is decomposed and dispersed, and is changed to polyphenylene and oxazole by a dehydration cyclization reaction, whereby heat resistance is obtained. As the heat treatment device, a heating plate, a supply box, and a temperature-increasing oven capable of setting a temperature control program can be used. As the ambient gas for heat treatment, air can be used, and an inert gas such as nitrogen or argon can also be used. When it is necessary to heat-treat at a lower temperature, it may be heated under reduced pressure using a vacuum spring or the like. The resin of the present invention can be compared with the prior PB 〇 precursor resin, 136993.doc 75- 200940601 at 250 ° C At this lower temperature, the polybenzoxazole completes the dehydration and cyclization ring closure reaction, and the mechanical elongation is also more than 4 Å. It is also better in improving the reliability of the semiconductor device. The formation method is combined with a known semiconductor device manufacturing method as a buffer film of a semiconductor device or a method of forming an interlayer insulating film, whereby a semiconductor device can be manufactured. EXAMPLES Hereinafter, examples of the embodiment of the present invention will be described in detail by way of Reference Examples, Examples and Comparative Examples. <Reference Example 1 &gt; (Bis(carboxy)tricyclo[5,2,1,〇 2,6] Manufacture of decane) In a glass separation three-necked flask equipped with an anchor stirrer manufactured by TEFLON (registered trademark), tricyclo[5,2,1,〇2,6]decane II was used. Methanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 71.9 g (〇.366 mol) dissolved in acetonitrile i [original, and dissolving disodium hydrogen phosphate 256 7 g in ion exchange water 1.4 L (1 8 〇 8 Φ Moule) ), sodium dihydrogen phosphate 217.i gd·809 mol) was added to the reaction/liquid mixture. 2,2,6,6-tetramethylenepiperidine·丨-oxyl radical (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "TEMp〇") was added thereto, and 搅拌 179 rm was added thereto. It dissolves. It was diluted with 850 ml of ion-exchanged water (80% sodium chlorite 143 2 as 丨267 mol), and added dropwise to the above reaction liquid. Then, 37 ml of a 5% aqueous sodium disulfite solution was diluted with 7 ml of ion exchange water, and added dropwise to the reaction liquid. The reaction solution was kept at 35 to 38 C by a constant temperature layer, and stirred for 20 hours to cause a reaction. 136993.doc -76- 200940601 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 liquid to make excess sodium sulfite. After passivation, it was washed with 500 ml of ethyl acetate. Thereafter, 115 ml of 10% hydrochloric acid was added dropwise, and the pH of the reaction mixture was adjusted to 3-4, 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, and the precipitate was dissolved in a tetrahydrofuran solution in the same manner. The above tetrahydrofuran solution was mixed, and dried over anhydrous sodium sulfate. The solution was concentrated and dried with an evaporator, whereby 58.4 g of bis(carboxy)tricyclo[5,2,1,02'6]decane (yield: 71.1%) of white crystals was obtained. The obtained bis(carboxy)tricyclo[5,2,1,02'6]nonane was analyzed by 1H-NMR and 13C-NMR, and it was confirmed that the alcohol was completely oxidized to a carboxylic acid. The results of 1H-NMR are shown in Fig. 1, and the results of 13C-NMR are shown in Fig. 2. The measurement conditions of each NMR are described below. I^H-NMR measurement conditions] ® Device: Varian Merccury MVX 300 MHz NMR Solvent: DMSO-d6 Measurement temperature: room temperature (25 ° C) [13C-NMR measurement conditions] Device·· BRUKER BIOSPIN Co., Ltd. Manufacturing Avance 600 spectrometer solvent • Dissolve the sample at 5 mass ° / ◦ in the γ-butyrolactone NMR sample tube: double pipe (inner tube: DMSO-d6 as Luo 136993.doc -77- 200940601 gram solvent (lock solvent), outer tube: sample solution) Determination method: complete proton decoupling method cumulative number: 3000 times measurement temperature: room temperature (about 25. 〇 &lt; reference example 2 &gt; in glass In a 100-mL three-necked flask, 2.71 g (15 mmol) of 5-aminoisophthalic acid (manufactured by MERCK) was dissolved in 沁methyl-2-pyrrolidone 30 g, pyridine. 2.37 g (30 mmol), and dropwise addition of 1.93 g of gas formate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 5.4 g of γ-butyrolactone (15.7 mmol was cooled to 0 in an ice bath) , adding sulfite emulsion 5 dissolved in 15 g of γ-butyrolactone in a manner of taking 3 〇 minutes and not exceeding l 〇 ° C 35 g (45 mmol). One side is cooled in an ice bath with no more than 1 Torr. While stirring for 1 hour, then returning to room temperature, the unreacted sulphur sulphur gas and by-products are distilled off using a vacuum pump. The sulfite gas is synthesized to synthesize a γ-aminoisophthalic acid derivative, which is referred to as a reaction liquid i. &lt;Reference Example 3&gt; In a separate three-necked flask made of glass, 1,3-phenylene Acetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 19.42 g (100 mmol), ^_methyl-2-pyrrolidone (hereinafter also referred to as "ΝΜΡ") 77 g, Ν, Ν-dimethyl 2 drops of guanamine were added to the reaction vessel, and the mixture was stirred and dissolved with a stirrer made of TEFLON (registered trademark). The reaction solution was cooled to -7 to -15 using a methanol bath cooled with dry ice. °C, and 28.56 g (240 mmol) of sulphur gas (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the reaction liquid, and then the reaction vessel was immersed in an ice bath and stirred for 1 hour. 136993.doc •78· 200940601 Further, using a vacuum pump, the unreacted sub-distillation was distilled off under reduced pressure for 30 minutes. Sulfur brewing gas and by-product sulfurous acid gas, thereby synthesizing hydrazine, 3-phenylene diacetate derivative, and using it as reaction liquid 2. <Reference Example 4> Using 1,4-phenylenediacetic acid (Tokyo) 19.80 g (115 mmol) manufactured by Huacheng Industrial Co., Ltd., in place of Reference Example 3, 13 phenylenediacetic acid (manufactured by Dong-Dong, Chemical Industry Co., Ltd.) 19 42 g (1 〇〇 millim) The same operation as in Reference Example 3 was carried out to synthesize a fluorene, 4-phenylene diacetate derivative. This was used as the reaction liquid 3. &lt;Reference Example 5&gt; Using a three-necked flask made of glass, 丨, 4·cyclohexanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 19.80 g (115 mmol), butyrolactone 60 g, gasified benzyl Triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 〇28 g (1.24 mmol) was added to a reaction vessel, and stirred with a stirrer made of tefl〇N (registered trademark) and a magnetic stirrer to dissolve . The reaction vessel was immersed in an ice bath &lt;cooled to 3 to 5 eC, and 32.84 g (276 mmol) of sulfinium chloride was added dropwise to the reaction solution, followed by agitation for 3 minutes. Further, an unreacted sulfite gas and a by-product sulfurous acid gas were distilled off under reduced pressure for 30 minutes using a vacuum pump to synthesize a 1,4-cyclohexanedicarboxylic acid derivative. This was used as the reaction liquid 4. <Reference Example 6&gt; In the 1 L separation flask equipped with a scrambler, a dropping funnel, and a thermometer, '4,4'-(1-(2-(4-)-phenylphenyl)-2-propyl group was used. a compound of phenyl)ethylene) bis (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Tris-PA) 30 136993.doc -79· 200940601 g (0.071 mol) as a polyhydroxy compound, which will be equivalent to the base The amount of μ 2 mol % of 1,2-naphthoquinonediazide 4 4 sulfonate 47 4 9 g (〇.m mol) is dissolved and dissolved in propylene g, and then using a thermostatic bath, The flask was adjusted to 30C. Then, triethylamine 179 was dissolved in 18 g of acetone and added to a dropping funnel, which was added dropwise to the flask over 3 minutes. After the completion of the dropwise addition, the mixing was further continued for 30 minutes, and then hydrochloric acid was added dropwise thereto, and the mixture was further mixed for a minute to complete the reaction. Thereafter, filtration was carried out to remove triethylamine hydrochloride. The filtrate obtained here was stirred while being added dropwise to a 3 l beaker which was mixed with pure water 164 〇 Ο and 30 g of hydrochloric acid to obtain a precipitate. The precipitate was washed with water and filtered, and dried under reduced pressure of 4 (TC) for 48 hours to obtain a sensitizer (PAC-1). &lt;Reference Example 7&gt; An anchor type stirrer equipped with TEFLON (registered trademark) was used. A separate three-necked flask made of glass was used as a reaction vessel. In the reaction vessel, 131.0 g of di-tert-butyl dicarbonate and 780 g of γ-butyrolactone were added, and the mixture was slowly added dropwise at room temperature at room temperature. a solution of 3-aminopropyltriethoxydecane 132·8 g and butyrolactone 270 g. The reaction solution was heated to about 40° C. with the addition, and it was confirmed that carbonic acid gas was generated along with the reaction. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and then the reaction liquid was confirmed by high performance liquid chromatography (HpLC). As a result, the starting material was not detected, and the product was detected as a single peak with a purity of 98%. The following auxiliary solution (D-1) was obtained in the above manner. &lt;Reference Example 8&gt; In a separate flask 136993.doc-80 - 200940601 with a stirrer, a dropping funnel and a thermometer, 4, 4· was used. -(1-(2-(4-hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (Honzhou Chemical Industry) As a polyhydroxy compound, the compound (trade name: Tris_PA) is used as a polyhydroxy compound, and the amount of 1,2-naphthoquinonediazide-5 is equivalent to 3 moles of the oxime H group. - Continued helium gas 47.49 g (0.177 mol) was stirred and dissolved in 300 g of acetone, and then the flask was adjusted to 30 ° C using a thermostatic bath. Then, 179 g of triethylamine was dissolved in 18 g of acetone, and added to a dropping funnel, which was then added dropwise to the flask over 30 minutes. After the completion of the dropwise addition, the stirring was further continued for 30 minutes, and then hydrochloric acid was added dropwise thereto, and the mixture was further stirred for 3 minutes to complete the reaction. Thereafter, filtration was carried out to remove triethylamine hydrochloride. The filtrate obtained here was stirred while being added dropwise to a beaker of pure water "40 g and hydrochloric acid 30 § to obtain a precipitate. The precipitate was washed with water, filtered, and then dried at 4 (TC). The film was dried under reduced pressure for 48 hours to obtain a sensitizer (PAC-2). &lt;Reference Example 9&gt; In a 5-liter flask equipped with a stirrer, a dropping funnel and a thermometer, phthalic anhydride was added. Ear), gbl (y-butyrolactone) 147 8 g as a solvent and stirred, and the flask was adjusted to 30 C using a thermostatic bath. 7-Aminopropyltriethoxydecane 2214 g (〇i Mo) After the addition to the dropping funnel, it was added dropwise to the flask over 30 minutes, and stirred at room temperature for 12 hours to obtain a secondary auxiliary (D-2). <Reference Example 10> Agitator, drip was attached Add 3,3',4,4'-dimercapto ketone tetracarboxylic dianhydride 16.11 g (〇〇5 mol) to the 5 〇〇mL three-neck flask of the funnel and thermometer, and use GBL〇y_butyrolactone as solvent. ) 153 g and stir using the constant 136993.doc 200940601 to adjust the flask to 30. 丫 丝 丝 propyl triethoxy (tetra) Μ After adding Μ g (〇.i mole) to the dropping funnel, it was added dropwise to the flask at 3 G minutes, and stirred at room temperature for 12 hours to obtain a subsequent auxiliary (D_3). Reference Example 11 &gt ;

In a 5〇〇mLi flask with a stirrer, a dropping funnel and a thermometer, γ-aminopropyltriethoxydecane 22 14 g (〇丨莫耳), GBL as a solvent (ir-butin) Vinegar) 116.6 g and stirring 'Adjust the flask to 3 (TC. Add the isocyanate benzene vinegar u.9 g (〇) molar) to the dropping funnel, and add it to the dropping funnel for 30 minutes. In the flask, the liquid temperature was raised to 5 ° C. After stirring at room temperature for 12 hours, a subsequent auxiliary (d_4) was obtained. &lt;Reference Example 12&gt; (bis(gas carbonyl)tricyclo[5,2,1, 02,6] Manufacture of decane) The bis(carboxy)tricyclo[5,2,1,〇2,6] obtained in Reference Example 1 was calcined with 625 g (278 mmol) and sulfoxide. ML (1.33 mol), 吼4 ml (5. 〇 millimolar) was added to the reaction vessel, and the mixture was stirred at 25 to 50 ° C for 18 hours to react. After the reaction, the benzene was added. The excess sulfite gas is azeotroped with toluene under reduced pressure to concentrate to obtain an oily bis(gas carbonyl)tricyclo[5,2,1,02,6]decane 73.3 § (Yield is 1 〇〇./0). About the obtained double (chlorine) Carbonyl)tricyclo[5,2,1,〇2'6]decane, which was analyzed by ιΗ_NMR and 13C-NMR, and confirmed that the carboxylic acid completely became a ruthenium chloride. The results of W-NMR are shown in Fig. 3, The results of 13C-NMR are shown in Fig. 4. The measurement conditions of the respective NMRs are as follows.

Apparatus: Varian Merccury MVX 300 MHz NMR 136993.doc -82- 200940601 Solvent: CDC13 Measurement temperature: room temperature (about 25 ° C) [13C-NMR measurement conditions] Apparatus: Avance 6 manufactured by BRUKER BIOSPIN Co., Ltd. 〇 Spectrometer Solvent: Dissolve the sample at 5 mass% in the butyrolactone NMR sample tube: cannula (inner tube: DMSO-d6 as the lock solvent, outer tube: sample solution) © assay: complete proton decoupling The cumulative number of times of the method: 3,000 times of measurement temperature: room temperature (about 25 ° C) <Example 1> (Production of alkali-soluble resin) Separated glass made of a mistype-mixer made of TEFLON (registered trademark) In a three-necked flask, bis(3-amino-4-hydroxyphenyl)propene (manufactured by CLARIANT) (hereinafter also referred to as "BAP") 69.17 g (268 mmol), NMP 276 g, acridine 12.7 g (160 mmol) was added to the reaction vessel to install a nitrogen introduction tube, and the mixture was purged with nitrogen to dissolve it. After the BAP was dissolved, the reaction vessel was immersed in a container to which dry ice was added to methanol. Cooling in. The bis(gaso)tricyclo[5,2,1,02'6]decane 69.99 § (268 mmol) produced in Reference Example 12 was dissolved in puddle _ 280 g 'maintained at - ίο19C 'Add to the reaction vessel in 30 minutes. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at (^丨〇°c, and searched for 2 hours. Further, the addition of 29.65 g (375 mTorr) was added. 136993.doc -83 - 200940601 Ethanol was added to the reaction solution, and the polymer was precipitated, and then recovered and dissolved in 350 ml of NMP. Then, 78 g of cation exchange resin (AMBERLYST A21, manufactured by ORGANO Co., Ltd.) and anion exchange resin (manufactured by ORGANO Co., Ltd.) were used. , AMBERLYST 15) 75 g for ion exchange. The solution was added dropwise to 3 liters of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated, and recovered, appropriately washed with water, dehydrated, and vacuum dried to obtain a precursor containing PBO. A powder of an alkali-soluble resin of the material unit. 之一 One part of the solution is diluted in N-methylpyrrolidone by high performance liquid chromatography (hereinafter also referred to as "GPC") (Shodex KD, manufactured by Showa Denko) -806M, KD-806M, tandem development solvent N-methylpyrrolidone 40 ° C) The molecular weight and molecular weight distribution were determined. The analysis conditions of GPC are as follows. Column: Showa Electric Co., Ltd. Shodex 805M/806M Tandem Dissolution: N-Mercaptopyrrolidone 40°C ® Flow Rate: 1.0 mL/min Detector: Japan's Spectroscopic Corporation's trade name RI-930 The weight average molecular weight of the molecular weight in terms of polystyrene ( Mw) is a single sharp curve of 36800, which is a single composition. γ-butyrolactone is added to the alkali-soluble resin, and the solvent-soluble resin solution having a resin concentration of 35 mass% is adjusted (Ρ-1). Example 2&gt; The bis(chlorocarbonyl)tricyclic ring of Example 1 was replaced with 69.99 g (268 mmol) 136993.doc -84- 200940601 [5,2,1,02'6]decane 66.25 8 (253.7 mmol) The same procedure as in Example 1 was carried out to obtain a PBO precursor having a weight average molecular weight (Mw) of 28,500 in terms of polystyrene, and γ-butyrolactone was added to the test-soluble resin to obtain Alkali-soluble resin solution (Ρ-2) of 35 mass% resin concentration. &lt;Example 3&gt; The bis(gas carbonyl) tricyclo[5,2,1 in Example I was replaced with 69.99 g (268 mmol). , 〇 2'6] decane 73.7 g (282 mmol), performing the same operation as in Example 从而A PBO precursor having a weight average molecular weight (Mw) of 53,745 in terms of a polystyrene-converted molecular weight was obtained, and 7-butylic vinegar was added to the alkali-soluble resin to obtain a solvent-soluble resin solution having a resin concentration of 35 mass% (P). -3) 〇&lt;Example 4&gt; A reaction vessel was a glass separation three-necked flask equipped with an anchor type stirrer made of TEFLON (registered trademark). In the synthesis, nitrogen gas was introduced while stirring. Add BAP 38.75 g (150 mmol), NMP 154 g, 0 to 7.12 g (90 mmol) to the reaction vessel, stir it under nitrogen, dissolve it, and dissolve the BAp. The reaction vessel was immersed in a vessel to which dry ice was added to methanol for cooling. The total amount of the reaction liquid 1 produced in Reference Example 2 (5-aminoisophthalic acid derivative 15 mmol) was maintained at -19 to 23, and all was added dropwise to the above reaction liquid. Then, the bis(gas carbonyl)tricyclo[5,2,1,02'6]nonane 35.29 g (135 mmol) produced in Example 2 was dissolved in γ·butyrolactone 11 〇g. Medium, kept at _19~ -23 °C ' and added dropwise to the reaction vessel. After the completion of the dropwise addition, the reaction vessel 136993.doc • 85 · 200940601 was added to the ice bath, kept at 〇 10 ° C, and stirred for 2 hours. Further, pyridine was 16.6 g (210 mmol). A poor solvent was added to the above reaction solution, and the polymer was batch-extracted and then recovered, and dissolved in 300 ml of tetrahydrofuran. Following 叩, the cation exchange resin 51 g and the anion exchange resin 50 g were exchanged from +6 hexan. This solution was added dropwise to 2 liters of ion-exchanged water under high agitation, and the polymer was dispersed and precipitated by μ w 1 τ. The mixture was appropriately washed with water, dehydrated, and vacuum dried, and ▲ was obtained to obtain a powder of a ruthenium precursor. The weight average molecular weight (Mw) of the octagonal and liter knives in terms of polystyrene was 40,600. The lactone is added to the alkali-soluble resin, and the alkali-soluble resin solution having a resin concentration of 35 mass% is subjected to two or four (4). ^ &lt;Example 5&gt; Using the bis(gas carbonyl)tricyclo[521〇2,6]decane Μ? g (259.1 mmol) of Example i instead of 69.99 g (268 mmol), double (gas) After the end of the drip of the 丄 丄 癸 , , , , , 添加 添加 添加 添加 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝 肝After 2 hours, the same operation as in the example! was carried out to obtain a weight average molecular weight (heart) of the amount of the knife in terms of polystyrene! 9 followed by the predecessor. The γ-butane was added to the test-soluble resin to obtain a test solution (ρ_5) β of a resin concentration of h by mass. The result of 13 C-NMR of the obtained polymer is shown in Fig. 5 . <Example 6> A DyStark water separator was attached to a glass separation type three-necked flask equipped with a wrong type agitator manufactured by TEFLON (registered trademark) ((10) "(4) called) 136993.doc -86- Cooling tube of 200940601. Add bis(3,4-dicarboxyphenyl)ether dianhydride (manufactured by MANAC) 18.61 g (60 mmol), BAP 32.16 g (12 〇 millimolar). Further, add γ- 110 g of butyrolactone and 22 g of toluene were used as solvents. After heating to 4 ° C, the mixture was stirred at 100 rprn for 90 minutes under nitrogen atmosphere. Thereafter, NMP 150 g and pyridine 2.37 g (30 mmol) were added. Add to the reaction solution, and immerse in a vessel with dry ice added to methanol for cooling. Burn the bis(gas group) tricyclo[5,2,1,0 ' ] 13.05 g (50 mmol) Dissolved in 26 g of γ-butyrolactone, kept at -5 to -1 (TC, and all added dropwise to the above reaction solution. After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath to keep it in the 〇~1 〇〇C, the mixture was mixed for 2 hours. Further, pyridine 5.53 g (7 〇 millimolar) was added. Then, 5_ decenoic acid-2,3-anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. ( 2 Torr, stirred at 50 ° C for 20 hours. Thereafter, &amp;&lt;&gt; heating was started in an oil bath of 180 C, and the whole solution was stirred at 1 go rpm. In the reaction, the by-product water and The toluene was azeotroped and the water accumulated in the bottom of the reflux pipe was discharged every '30 minutes. After 2 hours from the heating, the temperature was returned to room temperature, and a poor solvent was added to the reaction liquid to precipitate the polymer, and then proceeded. The solution was dissolved in 3 ml of NMp, and then ion exchange was carried out with 5 〇g of a cation exchange resin and 5 〇g of an anion exchange resin. The solution was added dropwise to ion-exchanged water under an idling scramble. In the middle of the process, the polymer is dispersed and precipitated, and is appropriately washed with water, and the water is removed, followed by vacuum drying to obtain a powder of a copolymer of the precursor and the ?1, and finally a weight average molecular weight of a molecular weight in terms of polystyrene is obtained ( Mw) is a copolymer of 17,000 PBO precursor and ?1. γ-butyrolactone is added to the test-soluble resin, and the alkali-soluble tree 136993.doc-87-200940601 fat solution of 35 mass% resin concentration is adjusted ( P-6). &lt; Example 7 &gt; using the following compound: [Formula 89]

85.9 g (268 mmol) was substituted for the BAP 69.17 g (268 mmol) of Example 5, and then the same operation as in Example 5 was carried out to obtain a PBO precursor having a polystyrene equivalent weight average molecular weight (Mw) of 22,000. Things. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-13) having a resin concentration of 35 mass%. The results of 13 C-NMR of the obtained polymer are shown in Fig. 6. &lt;Example 8&gt; The following compound of Example 5 was used in place of 102.5 g (268 mmol) of BAP 69.17 g (268 mmol):

Then, the same operation as in Example 5 was carried out to obtain a PBO precursor having a molecular weight average molecular weight (Mw) of 24,000 in terms of polystyrene. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (P-14) of 35 mass% 136993.doc • 88 - 200940601 resin concentration. The results of 13C-NMR of the obtained polymer are shown in Fig. 7. <Example 9> The following compound 79.97 g (268 mmol) was used instead of the BAP of Example 6 69.17 g (268 mmol): [Chem. 91]

Then, the same operation as in Example 6 was carried out to obtain a PBO precursor having a weight average molecular weight (Mw) of 20,000 in terms of polystyrene. 7-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (P-1 5) having a resin concentration of 35 mass%. The results of 13C-NMR of the obtained polymer are shown in Fig. 8. <Example 1〇>

替代 The following compound 80.51 g (268 millimoles) was used instead of the BAP of Example 6 69.17 g (268 millimoles): [Chem. 92]

Then, the same operation as in Example 5 was carried out to obtain a PBO precursor 136993.doc-89-200940601 having a weight average molecular weight (Mw) of 21,000 in terms of polystyrene. 7-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-16) having a resin concentration of 35 mass%. The results of 13C-NMR of the obtained polymer are shown in Fig. 9. &lt;Example 11&gt; The following compound 75.12 g (268 mmol) was used instead of the BAP of Example 6 69.17 g (268 mmol): [Chem. 93]

H2 Η [2ΝΗΟ

Then, the same operation as in Example 5 was carried out to obtain a PBO precursor having a weight average molecular weight (Mw) of 20,800 in terms of polystyrene. T-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (P-17) having a resin concentration of 35 mass%. The results of 13C-NMR of the obtained polymer are shown in Fig. 10. &lt;Example 12&gt; The bis(3-amino-4-hydroxyphenyl)sulfone 75.12 g (manufactured by Xiaoxi Chemical Industry Co., Ltd.) (268 mmol) was used instead of the BAP of Example 6 69.17 g (268 mmol) Then, the same operation as in Example 5 was carried out to obtain a PBO precursor having a weight average molecular weight (Mw) of 17,800 in terms of a molecular weight in terms of polystyrene. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-1 8) having a resin concentration of 35 mass%. &lt;Example 13&gt; 136993.doc -90· 200940601

The following compound 62.23 g (268 mmol) was used instead of the BAP of Example 5 69.17 g (268 mM): [Chem. 94]

Then, the same operation as in Example 5 was carried out to obtain a PBO precursor having a weight average molecular weight (Mw) of 23,000 in terms of polystyrene. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-19) having a resin concentration of 35 mass% / 。. The results of 13C-NMR of the obtained polymer are shown in Fig. 11. &lt;Example 14&gt; The following compound 75.00 g (231 mmol) (manufactured by Nippon Pure Pharmaceutical Co., Ltd.) was used instead of the BAP of Example 5, 69.17 g (268 mmol): [Chem. 95]

Then, the same operation as in Example 5 was carried out to obtain a PBO precursor having a molecular weight average molecular weight (Mw) of 16,000 in terms of polystyrene. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-20) having a resin concentration of 35 mass%. &lt;Comparative Example 1 &gt; A separable three-necked flask made of glass to which an anchor type stirrer manufactured by TEFLON (registered trademark) was attached was used as a reaction container. In the synthesis, one side access 136993.doc -91 - 200940601

Nitrogen was stirred while stirring. Bap 29.52 g (114 mmol), NMP 118 g, and pyridine 5.27 g (67 mmol) were added to the reaction vessel, and the mixture was stirred under a nitrogen atmosphere to dissolve. After the BAp was dissolved, the reaction vessel was immersed in a vessel to which dry ice was added to SOLMIX for cooling. The total amount of the reaction liquid 2 produced in Reference Example 3 (丨, 3 _ phenylenediacetic acid derivative 100 mmol) was maintained at -19 to -23. (:, and all the dropwise addition to the above reaction solution. 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, pyridine 1 〇 6 g (134 m) was added. Ethyl alcohol was added to the reaction solution, and the polymer was precipitated, recovered, and dissolved in 300 ml of NMP, followed by ion exchange with 5 g of a cation exchange resin and 50 g of an anion exchange resin. Under high-speed stirring, the solution was added dropwise to 2 liters of ion-exchanged water, and the polymer was dispersed and precipitated, and recovered, and washed with water, dehydrated, and then vacuum-dried to obtain a powder of a PBO precursor. A PB0 precursor having a weight average molecular weight (Mw) in terms of ethylene and having a molecular weight (Mw) of 21,000. Butyrolactone is added to the alkali-soluble ◎ resin, and if it is left overnight, it gels. Therefore, the alkali-soluble resin is dissolved in Ν-曱. In the pyrrolidone, an alkali-soluble resin solution (ρ_7) having a resin concentration of 35 mass% was obtained. <Comparative Example 2> BAP 27.98 g (108 mmol) was used instead of the comparative example jiBAp 29 52 g (l 14 mmol) ear) The same operation as in the comparative example was carried out except that the total amount of the reaction liquid 3 prepared in Reference Example 4 (the 1,4-phenylenediacetic acid derivative (115 mmol) was replaced by the reaction liquid 2). Thus, a pB〇 precursor 136993.doc • 92- 200940601 having a weight average molecular weight (Mw) of a molecular weight in terms of polystyrene of 3 丨 6 获得 is obtained. γ _ vinegar is added to the alkali-soluble resin, if placed One night, it gelled. Therefore, the alkali-soluble resin was dissolved in Ν-methylpyrrolidone' to obtain an alkali-soluble resin solution (ρ_8) having a resin concentration of 35 mass%. <Comparative Example 3 &gt; Using BAP 3 1.56 g (l22 mmol) instead of the comparative example jiBAp 29.52 g (l 14 mmol), using the total amount of the reaction liquid 4 prepared in Reference Example 5 (1,4-cyclohexanedicarboxylic acid derivative 115 m) In place of the reaction liquid 2, the same operation as in Comparative Example 1 was carried out to obtain a PB 〇 precursor having a weight average molecular weight (Mw) of 183 Å in terms of polystyrene-converted molecular ❹ *. Add γ·butyrol vinegar, if it is left overnight, it will be kneaded. So it will dissolve in alkali. The resin was dissolved in hydrazine-methylpyrrolidone to obtain an alkali-soluble resin solution (ρ_9) in a mass% resin concentration. <Comparative Example 4> An anchor type stirrer manufactured by TEFLON (registered trademark) was attached. In a separate three-necked flask made of glass, a nitrogen gas introduction tube and a thermometer were attached, and the flask was immersed in an oil bath while stirring with nitrogen, and stirred at 1 rpm. The bis(3·amino-4-hydroxy group) was added. Phenyl)sulfone 78 48 g (manufactured by Xiaoxi Chemical Industry Co., Ltd.) (280 mmol) (hereinafter also referred to as "s〇2H〇AB") is added to ΝΝ·dimethylammonium 300 g, pyridine 14·7 〇〇2-HOAB was dissolved in g〇87 mmol. The reaction solution was cooled to ❶4,4,_ oxybenzoyl chloroform (manufactured by Nippon Agricultural Co., Ltd.) (hereinafter also referred to as "DEDC") 73 45 g (10) millimolar) dissolved in γ-butyrolactone 2〇〇g The mixture was filled in a dropping funnel and added dropwise to the reaction liquid over 5 minutes. After the completion of the dropwise addition for 3 minutes, pyridine I36993.doc • 93· 200940601 29.4 g (374 mmol) was added. Mix for 2 hours at room temperature. Add 5-2, 3-Dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), heart g (62 mmol), and pass nitrogen gas on one side, and heat it at H) 〇 rpm under 5 〇 bath temperature. Mix for 8 hours. Thereafter, the glass tube was filled with a cation exchange resin substituted with NMP 500 g and a cation exchange resin of 1 〇〇g each. The above reaction droplets were added to 3 L of water under high-speed stirring to disperse and precipitate the polymer, and to recover it.

After appropriate washing with water and dehydration, vacuum drying is carried out to obtain a powder of an alkali. The weight average molecular weight (MW) of the molecular weight in terms of polystyrene is a sharp curve of 单, which is a mono-composition. Add 7-buty vinegar to the test-soluble resin, and gel it if left overnight. Therefore, the test-soluble resin is dissolved in N-methylpyrrolidone to obtain an alkali-soluble resin solution having a resin concentration of h% by mass (p_i. <Comparative Example 5> An anchor made of TEFLON (registered trademark) is attached. A three-way flask made of glass in a stirrer is equipped with a cooling tube attached with a Ding Stark water separator. Adding a second ring (2, 2, 2) - Xin Dongshui_2, 3, 5, 6_4 Formic acid Erye (manufactured by Tokyo Chemical Industry Co., Ltd.) 14.89 g (60 mmol), 4,4-diaminophenyl ether (manufactured by Wakayama Seiki Co., Ltd.) 6·01 g (3 〇 mmol) Further, 95.5 g of γ-butyrolactone and 30 g of toluene were added to the system as a solvent. The mixture was stirred at 1 rpm for 2 minutes at room temperature under a nitrogen atmosphere, and then immersed in an oil bath of 18 ° C. The heating was started, and the whole solution was stirred at 丨80 rpm. In the reaction, the by-product water was azeotroped with toluene and distilled off every 3 minutes, 136993.doc • 94· 200940601 was discharged at the bottom of the reflux tube. Water. After 2 hours after heating, the addition of the second stage was started, and bis(3-amino-4-hydroxyphenyl)sulfone 16.82 g (60 mM) was added. The ear was stirred for 1 hour. Then, 15.34 g (49.5 mmol) of bis(3,4-dicarboxyphenyl)ether dianhydride was added to the system. The mixture was heated and stirred at 180 rpm for 3 hours at i8 °C. After the removal from the oil bath, the heating is stopped. In the reaction, the water and toluene fractions of the by-product of the reaction are removed. The alkali-soluble resin produced as described above has a weight average molecular weight of 1200 in terms of polystyrene (^). Thus, an alkali-soluble resin solution (p_ ❹ 11) having a resin concentration of 35 mass% was obtained. &lt;Comparative Example 6&gt;

The same operation as in Comparative Example 4 was carried out by using BAP 72.28 g (280 mmol) instead of s〇2_h〇aB 78.48 g (280 mmol) of Comparative Example 4, thereby obtaining a weight average molecular weight in terms of polystyrene. An alkali-soluble resin having a molecular weight (Mw) of 14,000. To the alkali-soluble resin, 丫-butyrolactone was added and dissolved to obtain 35 ° /. A resin-soluble alkali-soluble resin solution (ρ_12). 〇 &lt;Comparative Example 7&gt; Using bis(3-amino-4-hydroxyphenyl)hexafluoropropane 1 〇 2 55 g (28 〇 millimolar) instead of S02-H0AB of Comparative Example 4 78.48 g (280 mmol) The same operation as in Comparative Example 4 was carried out to obtain an alkali-soluble resin having a weight average molecular weight (1^" of 155 Å in terms of polystyrene-converted molecules. In the base, γ_丁 was added to the tree The lactone was dissolved to obtain an alkali-soluble resin solution (Ρ-21) having a resin concentration of 35. <Examples 15 to 28, Comparative Examples 8 to 14> 136993.doc -95· 200940601 (Positive type photosensitive resin) Preparation of the composition) According to the combination of the following Table 1, the bath-like resin solution (p_〖~p_2丨) obtained in each of the above Examples 14 and Comparative Example 17 was purely separated from the alkali-soluble resin. 100 parts by mass, 22 parts by mass of the photosensitive diazophthalein compound PAC-1 obtained in Reference Example 6 was dissolved, and then 4 g parts of 5-n-hexyl resorcin (manufactured by Wako Pure Chemical Industries Co., Ltd.) was dissolved, and further After adding and dissolving 3 parts by mass of the auxiliary solution obtained in Reference Example 7, it was carried out with a translucent reactor. The positive-type photosensitive resin composition is obtained. © <Measurement of glass transition temperature (Tg) of cured film of positive photosensitive resin composition> By spin coater (C-made by Tokyo Electronics Co., Ltd.) ean Track Mark7 The positive photosensitive resin compositions obtained in the above Examples 15 to 28 and Comparative Examples 8 to 14 were applied onto a 6-inch wafer, and dried at 180 ° &lt;&gt; Using a temperature-raising oven (VF 200B manufactured by K〇y〇 Therm〇SyStem Co., Ltd.), under a nitrogen atmosphere, a heat-resistant cured film having a film thickness of 10.0 μm was obtained by heating at 32 (: The cured film was cut into a width of 3 mm, and immersed in a hydrofluoric acid aqueous solution for one night, and the film was peeled off and dried. For the obtained product, a Dinghe eight device (TMA_5〇 manufactured by Shimadzu Corporation) was used, and nitrogen flow was performed. The glass transition temperature was measured at a temperature rise rate of 10 〇 ml/min and a temperature increase rate of 10 ° t / min. The results are not shown in Table 2. In addition, 'in the evaluation of the following positive photosensitive resin composition' For the comparative example in which the sensitivity cannot be observed, it is not measured. &lt;Measurement of i-line permeability of mercury lamp for test-soluble resin&gt; Further, the test solution of 136993.doc-96-200940601 obtained in each of Examples 1 to 14 and Comparative Examples 1 to 7 was subjected to a solvent. Diluted and adjusted so that the alkali-soluble resin concentration was 1% by mass, and it was filled in a quartz photocell of 丨cm, and the i-line of the mercury lamp, that is, 365 nm, was measured by a UV-1600PC absorbance measuring machine manufactured by Shimadzu Corporation. Absorbance (calculated according to Lambert Beer's formula). The results are shown in Table 2. &lt;Evaluation of Positive Photosensitive Resin Composition&gt; (1) Patterning characteristics were evaluated on a 6-inch dream wafer, and the above-mentioned positive-type photosensitive was applied by a spin coater (Clean Track Mark 7 manufactured by Tokyo Electronics Co., Ltd.) The resin composition 'dried at 130 ° C for 180 seconds to obtain a coating film having a film thickness of 7.9 μm. On the coating film 'by the i-line stepper exposure machine (NSR 2005i8A manufactured by ΝΙΚ〇Ν )) 'through the main reticle, the exposure is changed by a mJ/cm2 per stage of exposure amount β 2 〇 /〇tmAH aqueous solution (Az 3〇〇MIF manufactured by CLARIANT), at 23. The developing time was adjusted under the conditions of 〇, and the wafer was developed to have a film thickness of 6.75 μm after development, and rinsed with pure water for 15 seconds to obtain a positive undulating pattern. The undulating pattern was observed with a microscope, and the minimum exposure amount of a 3.5 μm square undulating pattern capable of dissolving and removing the exposed portion was defined as the sensitivity, and the results are shown in Table 2. Into @, the coating film having a film thickness of 7.9 μm before development and a film thickness of 0.2 μm each is added under the condition that the minimum exposure amount obtained when the initial film thickness is 7·9 μΓη is added. Exposure 'Development time, fixed to the development time determined at an initial film thickness of 7 9 pm, developed, and found: when the thickness is increased relative to the original 136993.doc -97- 200940601 7.9 μηι The thickness of the undulating pattern is marginal. Can dissolve the square of 3_5 μηι

The positive photosensitive resin composition of Comparative Example 8 to U could not be adjusted by using γ-butyrolactone. The positive photosensitive resin composition of Comparative Example 8 to η was developed with a minimum development time of the developing machine, that is, 9 seconds, but the dissolution rate of the unexposed portion was very fast, and the film thickness after development could not be adjusted to 6.75 μΠ1. Unable to get the desired undulating pattern. This is because, in the unexposed portion, the dissolution of the insoluble resin by the naphthalene contained in the pACM cannot be suppressed, and as a result, the difference in the dissolution rate between the unexposed portion and the exposed portion cannot be obtained. In Comparative Examples 12 and 14, the desired pattern of 3 $ was obtained, but the sensitivity required to obtain the pattern was lower. In Comparative Example i 3, the film thickness was adjusted by adjusting the development time so as to reach 6 75 μηι Å but the desired pattern could not be obtained with an exposure amount of 8 〇〇 mj/cm 2 or less. In Comparative Example 14, the film thickness was adjusted by adjusting the development time so as to reach 6.75 μm and had a higher sensitivity 'but the ρ atom 0 having a halogen atom was used in Examples 15 to 28. A undulating pattern having a good film thickness at the time of processing with the same development time and the same exposure amount without a halogen atom is obtained. &lt;Preparation of hardening undulation pattern&gt; An undulating pattern obtained in Examples 15 to 28 was attached at 320 ° C in a nitrogen atmosphere using a temperature rising oven (manufactured by Koyo Thermo Systems, Inc., 2 〇〇 B). The crucible wafer was heated for 1 hour to obtain a hardened relief pattern having a film thickness of 5 μη. In particular, the shape of the undulating pattern of Examples 19 to 28 • 98-136993.doc 200940601 The pattern after the development of the image was excellent in pattern shape. This is due to the effect of the end of the polymer being sealed by 5-norborneuric anhydride. &lt;Evaluation of Optimum Solvent&gt; In the same manner as in Example 19, except that the polymer (Ρ-5) obtained in Example 5 was dissolved in the agent shown in Table 3 instead of GBL. Positive sensitization steep tree month's evaluation of patterning characteristics. At this time, the flatness of the coating film before development was taken out. The 7-point diameter on a 6-inch wafer is measured to determine the difference between the maximum film thickness and the minimum film thickness, which is divided by the 7-point flat film thickness (defined as surface smoothness). ) is shown in Table 3. The smaller the value, the better the surface smoothness. With respect to the acetone of Example 33, since the solvent was immediately dispersed during the coating process, the coating film was formed into a star shape and was not uniformly coated on the Shi Xi wafer. The butyl acetate of Example 34 did not dissolve the resin, so that the composition could not be produced. Further, the composition was allowed to stand at room temperature for 2 weeks while being opened in the air to obtain a viscosity change rate of the composition. The NMP of Example 30 and the dimethyl acetamide of Example 31 were whitened and turbid in a large amount after 2 weeks due to the influence of moisture in the air enthalpy. In Examples 32 and 33, the viscosity of the composition increased. The GBL of Example 29 is superior in terms of flatness, sensitivity, film thickness margin, and stability of the coating film. &lt;Evaluation of the preferred alkoxydecane compound&gt; In the alkali-soluble resin solution obtained in each of the above-mentioned Example 5, the photosensitivity obtained in Reference Example 6 was dissolved in an amount of 1 part by mass based on the pure fraction of the test resin. 22 parts by mass of the diazonaphthoquinone compound PAC-1, and then dissolved 4 parts by mass of 5_n-hexyl resorcinol (manufactured by Wako Pure Chemical Industries, Ltd.), and added and dissolved in the combination of the following Table 4, Reference Example 7, The auxiliaries obtained in 丨丨 136993.doc •99· 200940601 / 3 parts by mass of the combined liquid, or 6 parts by mass of the slick coupling agent sold after the squid; the filter is filtered to obtain positive photosensitivity Resin composition. In the same manner as in the above-described Example 19, the patterning characteristics were evaluated, and a pattern having an exposure amount of 100 mJ/cm 2 higher than the minimum exposure amount was observed, and five lengths of the 歹J were 丨em: 丨之The pattern of the line and the gap was observed, and the line and gap pattern of the minimum size which are all completely followed by five were defined as the minimum following pattern, and the adhesion of the pattern at the time of development was compared. The results are shown in Table 5. In this case, the line of the smaller size and the developer of the gap are better. In Examples 35 to 43, a smaller pattern of 3 microns or less was followed. Further, the positive photosensitive resin composition obtained in Examples 35 to 46 was applied onto a 6-inch wafer by a spin coater (Clean Track Mark 7 manufactured by Tokyo Electronics Co., Ltd.), and dried at 130 ° C. After that, the mixture was heated at 320 ° C for 1 hour in a nitrogen atmosphere using a temperature-raising oven (VF 200B manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a heat-resistant cured film having a film thickness of 10.0 μm. The sample after the formation of the cured film was treated in a pressure cooker (131 ° C, 3 Torr) for 1 〇〇 hour, and then a crutch scis cut test (JIS K5400) was used as a cutter knife. Scratches are formed to form 100 squares of 1 mm square, which are peeled off from top to bottom with Cellophane (registered trademark) tape, and are discarded without being attached to celluloid (registered trademark) tape. The number of squares on the substrate was used to evaluate the water resistance. Table 5 shows the number of squares remaining on the tantalum wafer after the tape peeling test. The more the number, the better the next. The film after curing of Examples 35 to 43 was excellent in water resistance. Examples 35 to 43 136993. doc - 100 · 200940601 It is more preferable because all of the adhesion of the pattern after development, the subsequent adhesion to the ruthenium wafer after thermosetting, and the storage stability of the photosensitive resin composition are satisfied. &lt;Evaluation of the compound which causes the crosslinking reaction by the heat&gt; In the alkali-soluble resin solution (p_5) obtained in each of the above-mentioned Example 5, the reference example 5 was dissolved in 100 parts by mass of the pure fraction of the test-soluble resin. 22 parts by mass of the photosensitive diazo naphthalene compound PAC-1 obtained, and then dissolving 4 parts by mass of 5_n-hexyl stupid (manufactured by Wako Pure Chemical Industries, Ltd.), and adding the obtained in Reference Example 7 The auxiliary solution was dissolved in 3 parts by mass, and the compound which caused the crosslinking reaction by heat was dissolved in a combination of the following Table 6, and then filtered using a 1 pm reactor to obtain a positive photosensitive resin composition. The evaluation of the patterning characteristics was carried out in the same manner as in the above Example 19. The results are shown in Table 7. Using a temperature-raising oven (VF 200B manufactured by K〇y〇 Thermo System, Inc.), a heat-resistant cured film was obtained by heating the patterned patterned stone wafer in the nitrogen atmosphere for 1 hour under a nitrogen atmosphere. After measuring the film thickness of the heat-resistant cured film of the patterned ruthenium wafer, the etched wafer is heated to 8 〇〇C and filled with anti-surname stripping solution TOK 105 (Tokyo Chemical Industry Co., Ltd.) The product was immersed in a bath for 3 minutes, and after washing with pure water, the film thickness was measured to measure the residual film ratio. The state of the pattern was observed. The results are shown in Table 7. Further, with the examples In the same manner, the glass transition temperature (Tg) of the cured film of the positive photosensitive resin composition was measured. The results are shown in Table 7. Further, the respective photosensitive resin compositions were placed at room temperature. The viscosity change rate after 4 weeks was measured. The results are also shown in Table 7. The glass transition temperatures of Examples 47 to 62 were higher than those of Example 63, and the glass transition temperature was also 136,993.doc -101 - 200940601. Chemical resistance is also improved, so it is better. In the seventh, CL-1 to CL-13 are as follows: [Chem. 96] CL-1 Sanwa Chemical Co., Ltd. is manufactured under the trade name of NIKALAC MW 390 H3COH2C'n/CH2OCII3 ii3coii2c, m/^n person]^ch2och3 H3COH2C ClhOCll,

CL-2 Sanwa Chemical Co., Ltd. is manufactured under the trade name NIKALAC MX 290 i? h3coh2c-nh-c-nh-ch2och3 [Chem. 98] CL-3 Sanwa Chemical Co., Ltd. is manufactured under the trade name NIKALAC MX. 280 1 H3COH2- N ^ N -ch2och3

CH3o OCH3 [Chem. 99] CL-4 Sanwa Chemical Co., Ltd. is manufactured under the trade name NIKALAC MX 270 136993.doc -102· 200940601

H3COH2C J\ yCH2OCH3 'N N

M N...N% H3COH2C' 丫 CH2〇CH3 o [Chem. 100]

CL-5 Honshu Chemical Industry Co., Ltd. is manufactured under the trade name TMOM-BP

,ch2oc&quot;3

[化101]

CL-6 Honshu Chemical Industry Co., Ltd. is manufactured under the trade name DMOM-PTBP

OH

[化102]

CL-7 Honshu Chemical Industry Co., Ltd. is manufactured under the trade name DMOM-PC.

[Chem. 103] CL-8 Tokyo Chemical Industry Co., Ltd. manufactures 2,2-bismethoxymethylbiphenyl ch3-o-ch2

CH2-0-CH3 136993.doc -103- 200940601 [Chem. 104]

CL-9 Maruzen Petrochemical Industry Co., Ltd. is manufactured under the trade name BANI-X

CL_10 Maruzen Petrochemical Industry Co., Ltd.

BANI-M

[化106] CL-11 East Asia Synthetic Co., Ltd. made the trade name tear-(1)

[Chem. 107] The product name is OXT-221 CL_12 East Asia Synthetic Co., Ltd.

2,2-bis(4-glycidoxyoxy CL-13 manufactured by Tokyo Chemical Industry Co., Ltd.) phenyl 136993.doc -104- 200940601

&lt;Evaluation of at least one compound selected from the group consisting of an acrylate compound, a mercapto acrylate compound, an allyl group-containing compound, a methoxy group-containing compound, and a benzene vinegar compound group 1&gt; In the alkali-soluble resin solution (p_5) obtained in Example 5, 12 parts by mass of the photosensitive diazonaphthoquinone compound PAC-1 obtained in Reference Example 5 was dissolved in 1 part by mass of the alkali-soluble resin. 30 parts by mass of the co-agent solution obtained in the reference example 7 in Example 7, CL-8 6 parts by mass, CL_9 4 parts by mass, and 6 parts by mass of methoxyphenylacetic acid were dissolved, and then selected from the combination shown in Table 8, At least one compound selected from the group consisting of an acrylate compound, a mercapto acrylate compound, an allyl group-containing compound, a methoxy group-containing compound, and a phenyl ester compound, and is subjected to a filter using a filter of 丨μηη Thus, a positive photosensitive resin composition was obtained. The patterning characteristics were evaluated in the same manner as in the above Example ^9. The results are shown in Table 9. Further, the development time required at this time is also shown in Table 9. Using the temperature-increasing oven (vf 200 制造 manufactured by Koyo Thermo System), the thus obtained patterned ruthenium wafer was heated at 32 CTC for 7 hours under nitrogen atmosphere to obtain heat-resistant hardening of the pattern shape after development. membrane. Examples 64 to 76 are preferred in that the light sensitivity is high and the film thickness margin is wider. In Table 8, F-1 to F-7 are as follows: [Chem. 109]

F_1 and Wako Pure Chemical Industries, Ltd. manufactures the finished product TRIAM 70S 136993.doc -105· 200940601 / Plant 0-C II 〇 II ο [Chem. 110]

F-2 and Wako Pure Chemical Industries Co., Ltd. manufactures TRIAM

[Chem. 111] F_3 and Wako Pure Chemical Industries, Ltd. manufactures the finished product TRIAM 501 [Chem. 112]

© F-4 Shin-Nakamura Chemical Industry Co., Ltd. manufactured under the trade name of 4 EG

[化113]

F-5 New Nakamura Chemical Industry Co., Ltd. manufactured under the trade name of 9 EG

136993.doc -106- 200940601 {where n 2 is an integer from 1 to 20, with an average of 9} [Chem. 114] Tokyo Chemical Industry Co., Ltd. manufactured under the trade name of 1,3,5-trimethoxybenzene OCHj [Chem. 115] F-7 Tokyo Chemical Industry Co., Ltd. manufactures h3c^〇hQkhQk〇-L3 &lt;Evaluation of monocarboxylic acid compound&gt; In the alkali-soluble resin solution (p-5) obtained in each of the above Examples 5, it is pure with respect to the alkali-soluble resin. After dissolving 12 parts by mass of the photosensitive diazonaphthoquinone compound PACd obtained in Reference Example 6_, 30 parts by mass of the auxiliary solution obtained in Reference Example 7 ^, CL_8 6 parts by mass, CL_9 tannin was dissolved. 6 parts by mass of the dissolution inhibitor F-丨 was added, and then a monocarboxylic acid compound was added in the combination shown in Table 1A, and filtered with a filter of 丨μηη to obtain a positive photosensitive resin composition. The patterning characteristics were evaluated in the same manner as in the above Example 19. Further, a pattern having an exposure amount of 1 〇〇mJ/cm 2 higher than the minimum exposure amount was observed, and a pattern of five lines and gaps having a length of 1 : 1 was observed, and the minimum size of all five was completely followed. The line and gap pattern is defined as the minimum rounding case, and the continuity of the pattern during development is compared. These results are shown in the table 丨. Further, the development time required at this time is also shown in the table. Use a warming oven (K〇y〇 136993.doc -107- 200940601

The VF 200B manufactured by Thermo System, Inc., was heated at 320 ° C for 1 hour in a nitrogen atmosphere to obtain a heat-resistant cured film which maintained the pattern shape after development. Examples 79 to 85 are preferred in that the sensitivity is high and the film thickness margin is wider. <Examples 89 to 99, and Comparative Examples 15 to 21 (Preparation of Negative Photosensitive Resin Composition) According to the combination of the following Table 12, the bases obtained in each of Examples 4 to 14 and Comparative Examples 1 to 7 were used. In the soluble resin solution (P_4~p_21), 2-[2-(4-©methylphenylsulfonyloxyimino)-2,3-dihydrothiophene-3-ylidene-2-( 2-Methylphenyl)acetonitrile (Irgacure PAG 121, manufactured by CIBA. JAPAN) 5 parts by mass 'as a compound which generates an acid by irradiation with active light (PAG); dissolved CL-4: alkoxylated urea 30 parts by mass of resin (product number MX-270 'manufactured by Sanwa Chemical Co., Ltd., trade name: NIKALAC, monomer 95% or more) as a compound crosslinkable by the action of an acid; further added and dissolved in Reference Example 7 The resulting auxiliary solution D-1 30 parts by mass 'filtered with a filter of 1 Pm to obtain a negative photosensitive resin composition. &lt;Evaluation of Negative Photosensitive Resin Composition&gt; Evaluation of Patterning Properties The negative photosensitive resin composition obtained in the above Examples 89 to 99 and Comparative Examples 15 to 21 was spin-coated at 6 inches. On the wafer, and on the hot plate with 110. (: Baking for 3 minutes to obtain a film having a thickness of about 15 μm. The film was changed stepwise by the i-line stepper exposure machine (manufactured by Nippon Co., Ltd., NSR 2005i8A) 'through the main mask' Exposure amount into 136993.doc •108· 200940601 line exposure. Exposure of the exposed wafer to the exposed wafer at 120 °C for 3 minutes, using 2.3 8% of the butyl PCT solution ((: 1^111 Development was carried out by adding 2 300 MIF), and then rinsing with deionized water to obtain an undulating pattern. The undulating pattern was observed under a microscope to maintain the exposed area with a film thickness of about 90%. The exposure amount of the portion was set as the sensitivity (the minimum exposure amount), and the via size after the square undulation pattern of the unexposed portion was completely dissolved and removed was defined as the resolution. The results are shown in Table 13 below. Further, when the initial film thickness is increased from 15 μm to 0.5 μm each time, the minimum exposure amount and the development time obtained when the initial film thickness is 15 μm are fixed, and when the etching evaluation is performed, Find the developable film thickness Inter. The results are shown in Table 13. Comparative Example 15~21 89~99 compared with that having a high sensitivity, the film thickness of the marginal Example wider and more excellent in terms of a halogen-free. [Table 1]

Alkali-soluble resin photosensitive diazonium mixture organic solvent Example 15 Ρ-1100 parts by mass PAC-122 parts by mass GBL Example 16 Ρ-2100 parts by mass PAC-1 22 parts by mass GBL Example 17 Ρ-3100 parts by mass PAC- 122 parts by mass GBL Example 18 Ρ 4100 parts by mass PAC-122 parts by mass GBL Example 19 Ρ-5100 parts by mass PAC-122 parts by mass GBL Example 20 Ρ-6100 parts by mass PAC-122 parts by mass GBL Example 21 Ρ-13100 Parts by mass PAC-122 parts by mass GBL Example 22 Ρ-14100 parts by mass PAC-122 parts by mass GBL Example 23 Ρ-15100 parts by mass PAC-122 parts by mass GBL Example 24 Ρ-16100 parts by mass PAC-122 parts by mass GBL Example 25 Ρ-17100 parts by mass of PAC-122 parts by mass GBL Example 26 Ρ-18100 parts by mass PAC-122 parts by mass GBL Example 27 Ρ-19100 parts by mass PAC-2 22 parts by mass GBL Example 28 Ρ-20 100 Parts by mass PACM 22 parts by mass GBL Comparative Example 8 Ρ-7100 parts by mass PAC-122 parts by mass NMP 136993.doc -109- 200940601

Comparative Example 9 P-8100 parts by mass of PAC-122 parts by mass of NMP Comparative Example 10 P-9100 parts by mass of PAC-122 parts by mass of NMP Comparative Example 11 P-10100 parts by mass of PAC-122 parts by mass of NMP Comparative Example 12 P-11100 parts by mass PAC-122 parts by mass GBL Comparative Example 13 P-12100 parts by mass PAC-122 parts by mass GBL Comparative Example 14 P-21100 parts by mass PAC-122 parts by mass GBL

[Table 2]

Minimum exposure of I-line exposure (mJ/cm2) Tg 0C) Development initial film thickness margin (/m) Absorbance at 365 nm of alkali-soluble resin Fluorine atom % in alkali-soluble resin Example 15 200 240 1.0 0.018 0% Implementation Example 16 300 239 1.4 0.024 0% Example 17 200 240 1.0 0.016 0% Example 18 250 249 1.4 0.016 0% Example 19 275 244 1.4 0.017 0% Example 20 275 295 0.8 0.109 0% Example 21 275 261 1.2 0.028 0% Example 22 275 265 1.4 0.024 0% Example 23 300 248 1.4 0.059 0% Example 24 275 252 1.2 0.032 0% Example 25 275 262 1.4 0.025 0% Example 26 350 247 1.4 0.006 0% Example 27 275 245 1.0 0.109 0% Example 28 325 245 1.4 0.054 0% Comparative Example 8 Unobservable - 0.112 0% Comparative Example 9 Unobservable - 0.323 0% Comparative Example 10 Unobservable - 0.016 0% Comparative Example 11 Unable to observe 0.098 0 % Comparative Example 12 525 297 0.6 0.122 0% Comparative Example 13 &gt; 800 - 0.945 0% Comparative Example 14 350 295 0.4 0.182 18% 110- 136993.doc 200940601 ο [εί Composition viscosity change rate +2.4% | -1.6% | -3.5% | +12.5% | +83% | Unable to evaluate 1 surface Slipability 0.0127 0.0265 0.0185 0.1492 Unable to evaluate the unrecognizable ns 1 〇 — 〇〇 Unable to evaluate the minimum exposure (mJ/cm2) fS 350 350 350 Unable to evaluate the unsolvable solubility to $ Ϊ Insoluble solvent Solvent GBL NMP Ethylamine cyclohexanone acetone 1 butyl acetate I | Example 29 | Example 30 | Example 31 | Example 32 | Example 33 | Example 34 136993.doc -Ill - 200940601 Alkoxyl compound 30 parts by weight of D-1 solution | D-2 solution 20 parts by weight of D-3 solution 10 parts by weight | D-3 solution 30 parts by weight | D-4 solution 30 parts by weight | tie* &lt;&lt; 輙Μ 齚i 4uft % Φ , , 1 P § Cabinet W &lt;&lt; % t/) S «fs »-gg ”1 wa K N-(3-triethoxydecylpropyl)urea (product manufactured by AZMAX Co., Ltd.) Named SIU 9055.0) 6 parts by weight of 3-(m-aminophenoxy)propyltrimethoxydecane (trade name SLA 0598.0, manufactured by AZMAX Co., Ltd.) 6 parts by weight of 2-(trimethoxydecylalkylethyl) Pyridine (trade name SIT 8396.0, manufactured by AZMAX Co., Ltd.) 6 parts by weight 裨id alkali ΙΪΓ &lt;&lt; Η Ϊ % ”1 umbrella 轼S ¢3 vinyl Triethoxy decane (trade name KBE 100, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by weight unadded 1 PAC-1 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight 22 parts by weight of polymer P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight P-5 100 parts by weight | Example 35 丨 Example 36 | Example 37 | Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 Example 45 | Example 46 136993.doc -112- 200940601 [Table 5] Minimum required exposure amount (mJ/cm2) Minimum amount of exposure + 100 mJ/cm2 minimum follow-up pattern high pressure money test 100 hr draw tape test development initial film thickness edge division (/ΛΠ) Example 35 275 1 100 1.4 Example 36 275 2 99 1.4 Example 37 275 3 99 1.4 Implementation Example 38 275 2 100 1.4 Example 39 275 1 98 1.4 Example 40 275 2 99 1.4 Example 41 275 3 100 1.4 Example 42 27 5 1 100 1.4 Example 43 275 1 97 1.4 Example 44 275 25 0 1.4 Example 45 275 40 0 1.4 Example 46 275 80 0 1.4 [Table 6]

Polymer PAC-1 Compound which causes exchange reaction by heat Example 47 P-5 100 parts by weight 22 parts by weight (Χ·110 parts by weight Example 48 P-5 100 parts by weight 22 parts by weight CL~2 10 weight Example 49 Ρ·5 100 parts by weight 22 parts by weight CL-3 10 parts by weight Example 50 Ρ-5 100 parts by weight 22 parts by weight CL4 10 parts by weight of Example 51 Ρ-5 100 parts by weight 22 parts by weight CL- 5 10 heavy Dong Example 52 Ρ-5 100 parts by weight 22 parts by weight CL-6 10 parts by weight Example 53 Ρ-5 100 parts by weight 22 parts by weight CL-7 10 parts by weight Example 54 Ρ-5 100 parts by weight 22 parts by weight of CL-8 10 parts by weight of Example 55 Ρ-5 100 parts by weight of 22 parts by weight of CL-9 10 parts by weight of Example 56 Ρ-5 100 parts by weight of 22 parts by weight of CL-10 10 parts by weight of Example 57 Ρ- 5100 parts by weight 22 parts by weight CL-1110 parts by weight Example 58 Ρ-5 100 parts by weight 22 parts by weight CL-12 10 parts by weight Example 59 Ρ-5 100 parts by weight 22 parts by weight CL~13 10 parts by weight Example 60 Ρ·5 100 parts by weight 22 parts by weight CL&gt; 4 5 parts by weight of Example 61 Ρ-5 100 parts by weight 22 parts by weight CL-4 20 parts by weight Example 62 Ρ-5 100 weight Dong 22 weight Part CL-4 30 parts by weight Example 63 Ρ-5 100 parts by weight 22 parts by weight not added 136993.doc •113- 200940601 [Table 7] Minimum required amount of azine light (mJ/cm2) 初始 initial film thickness edge|^〇 Om) glass transfer a degree 〇 c) chemical resistance test residue rate (%> chemical resistance test case SL4 back viscosity change example 47 325 1.4 272 100% no problem 13% implementation Example 48 300 1,4 263 100% No problem 5% Example 49 300 1.4 264 100% No problem 6% Example 50 300 1.4 268 100% No problem 6% Example 51 275 1.4 264 100% No problem 7 % Example 52 275 1.4 261 100% No problem 5% Example 53 275 1.4 259 100% No problem 5% Example 54 250 1.4 265 100% No problem 4% Example 55 250 1.4 259 100% No problem 4% Implementation Example 56 250 1.4 257 100% No problem 4% Example 57 275 1.4 260 100% No problem 6% Example 58 275 1.4 259 100% No problem 5% Example 59 350 1.4 255 100% No problem 16% Example 60 275 1.4 261 100% No problem 5% Example 61 325 1.4 269 100% No problem 8% Example 62 350 1.4 269 100% No problem 11% Example 63 275 1.4 24 498% of crack 4%

[Table 8] Polymer PAC-1 (F) Compound Example 64 P-5 100 parts by weight 12 parts Dong F-1 5 parts by weight Example 65 P-5 100 parts by weight 12 parts by weight F-11 parts by weight Example 66 P-5 100 parts by weight 12 parts by weight F-120 parts by weight Example 67 P-5 100 parts by weight 12 parts by weight - F-2 5 parts by weight Example 68 P-5100 parts by weight 12 parts by weight -歹-3 5 parts by weight of Example 69 P-5 100 parts by weight 12 parts by weight - Yin-4 5 parts by weight Example 70 P-5 100 parts by weight 12 parts by weight _F-4 10 parts by weight Example 71 P- 5 100 parts by weight 12 parts by weight - F-5 5 parts by weight Example 72 P-5 100 parts by weight 12 parts by weight Κ·6 5 parts by weight Example 73 P-5100 parts by weight 12 parts by weight IV7 5 parts by weight Example 74 P-5 100 parts by weight 12 parts by weight F-7 10 parts by weight Example 75 P-5 100 parts by weight 12 parts by weight &quot;f戍tetradecane triacrylate 5 parts by weight Example 76 P-5 100 parts by weight 12 weight Fractions Λ 四录 Diacrylic acid brewing W parts by weight Example 77 P-5100 parts by weight 12 parts by weight None Example 78 P-5100 parts by weight 20 parts by weight No 136993.doc -114· 200940601 [Table 9] PAC- 1 (F) Compound I 黍Minimum amount of Qin light (mJ/cm2) Requires shadow time (seconds) Shadow initial flag thickness margin um) Example 64 12 heavy Dong F-1 5 parts by weight 175 70 1·6 Example 65 12 parts by weight F - 110 parts by weight 175 82 1.6 Example 66 12 parts by weight F-1 20 parts by weight 150 98 1.4 Example 67 12 parts by weight F-2 S parts by weight 200 65 1.6 Example 68 12 parts by weight F-3 5 parts by weight 200 62 1.6 Example 69 12 heavy Dong F-4 5 parts by weight 175 68 1.6 Example 70 12 parts by weight F &gt; 4 10 parts by weight 150 75 1.6 Example 71 12 parts by weight F-5 5 parts by weight 200 74 1.6 Implementation Example 72 12 parts by weight F_6 5 parts by weight 200 66 1.6 Example 73 12 parts by weight F-7 5 parts by weight 175 71 1.6 Example 74 12 parts by weight F-710 parts by weight 175 85 1.6 Example 75 12 parts by weight F-8 Pentaerythritol triacrylate 5 parts by weight 175 74 1.6 Example 76 12 parts by weight of F-8 pentaerythritol triacrylate hydrazine 10 parts by weight ISO 86 1.4 Example 77 12 parts by weight not added 225 57 1.6 Example 78 20 Weight parts not added 250 85 1.4

[Table 10] Polymer PAC-1 iG) Compound having a carboxyl group in the molecule Example 79 Ρ-5100 parts by weight 12 parts by weight citronellic acid 5 parts by weight Example 80 Ρ-5100 reset portion 12 parts by weight citronellic acid 10 weights Dongfang Example 81 Ρ-5 100 parts by weight 12 parts by weight citronellic acid 20 parts by weight Example 82 Ρ-5100 parts by weight 12 parts Dong methoxyphenyl acetic acid 5 parts by weight Example 83 Ρ-5100 weight 12 parts by weight of methoxyphenylacetic acid 10 parts by weight of Example 84 Ρ-5 100 parts by weight 12 parts by weight of m-toluic acid S parts by weight Example 85 PS 100 heavy Dong 12 parts by weight of m-toluic acid 10 parts by weight Example 86 Ρ-5 100 parts by weight 12 parts by weight acetic acid 5 parts by weight Example 87 Ρ-5 100 parts Dong 12 parts by weight acetic acid 10 parts by weight Example 88 Ρ-5 100 parts by weight 12 parts by weight not added 136993.doc 115- 200940601 [Table 11] PAC-1 (G) Compound I having a carboxyl group in the molecule I line exposure Minimum amount of xylazine light (mJ/cm2) Development time required (seconds) Development initial film thickness side division (/«*) Example 79 12 5 parts by weight of citronellic acid 175 72 1.6 Example 80 12 parts by weight of citronellic acid 10 parts by weight 175 65 1.6 Example 81 12 parts by weight of citronellic acid 20 parts by weight 175 59 1.4 Example 82 12 parts by weight of methoxyphenylacetic acid 5 parts by weight 175 69 1.6 Example 83 12 parts by weight of methane phenylacetic acid 10 parts by weight 175 65 1.6 Example 84 12 parts by weight of m-toluic acid 5 parts by weight 175 66 1.6 Example 85 12 parts by weight of m-toluic acid 10 parts by weight 175 60 1.6 Example 86 12 parts by weight acetic acid 5 parts by weight 250 71 1.6 Example 87 12 weight Partial acetic acid 10 parts by weight 250 65 1.6 Example 88 12 parts by weight not added 250 78 1.4 [Table 12]

Alkali-soluble resin PAG CL-4 D-1 Organic solvent Example 89 Ρ-4100 parts by mass 5 parts by mass 30 parts by mass 30 parts by mass GBL Example 90 Ρ-5100 parts by mass 5 parts by mass 30 parts by mass 30 parts by mass GBL Example 91 Ρ-6100 parts by mass S parts by mass 30 parts by mass 30-membered parts GBL Example 92 p-moo parts by mass 5 parts by mass 30 parts by mass 30 parts by mass GBL Example 93 Ρ·14 100 parts by mass 5 parts by mass 30 parts by mass 3 〇 parts by mass GBL Example 94 Ρ-15100 parts by mass 5 parts by mass 3 〇 parts by mass 30 parts by mass GBL Example 95 Ρ-16100 parts by mass 5 parts by mass 30 parts by mass 3 〇 parts by mass GBL Example 96 Ρ-17100 mass 5 quality Dong 30 30 quality Dong 30 quality Dong GBL Example 97 Ρ-18100 parts 5 quality Dong 30 parts 3 〇 董 Dong GBL ΪΓ Example 98 Ρ-19100 quality Dong 5 parts 30 quality Dongfen 3 〇质董份 GBL Example 99 Ρ-20 100 parts by mass 5 parts by mass 30 parts by mass 3 〇 parts by mass GBL Comparative Example 15 Ρ-7100 parts by mass 5 parts Dong 30 parts by mass 30 parts by mass NMP Comparative Example 16 Ρ-8100 parts by mass of 5 parts by mass of 3 parts by mass of 30 parts by mass of NMP Comparative Example 17 Ρ-9100 quality Dongs S quality 30 parts by mass of 3 parts by mass of NMP Comparative Example 18 Ρ-10100 parts by mass 5 parts by mass 30 parts by mass 3 parts by mass NMP Comparative Example 19 Ρ-11100 parts by mass 5 parts by mass 3 〇 parts by mass 3 〇 parts by mass GBL Comparative Example 20 Ρ-12 100蜇Dong S mass parts 3〇 parts by mass 3〇 parts by mass GBL Comparative Example 21 Ρ-23100 parts by mass 5 parts by mass Γ 30 parts by mass Γ30 parts by mass GBL 136993.doc •116, 200940601 [Table 13] Alkali Minimum exposure amount of soluble resin (mJ/cm2) Resolution 〇um) Development initial film thickness margin 〇um) Fluorine atom in alkali-soluble resin (%) Example 89 P-4 100 parts by mass 450 15 1.0 0 Example 90 P -5100 parts by mass 450 14 1.5 0 Example 91 P-6100 parts by mass 400 18 1.0 0 Example 92 P-13100 parts by mass 375 15 1.5 0 Example 93 P-14100 parts by mass 350 14 1.0 0 Example 94 P-15100 Parts by mass 375 15 1.5 0 Example 95 P-16100 parts by mass 400 14 1.0 0 Example 96 P-17100 parts by mass 450 16 1.5 0 Example 97 P-18100 parts by mass 600 10 1.0 0 Example 98 P-20100 parts by mass 450 18 1.0 0 Example 99 P-22100 parts by mass 500 17 1.0 0 Comparative Example 15 P-7 100 parts by mass 800 1 8 0.5 0 Comparative Example 16 P-8 100 parts by mass 900 20 0.5 0 Comparative Example Π P-9100 parts by mass 650 15 0.5 0 Comparative Example 18 P-10 100 parts by mass &gt; 1000 - 0 Comparative Example 19 P-11 100 mass Parts 850 18 0.5 0 Comparative Example 20 P-12100 parts by mass 950 25 0.5 0 Comparative Example 21 P-23100 parts by mass 600 15 0.5 18

[Industrial Applicability] The positive photosensitive resin composition of the present invention can be suitably used in the fields of a protective film for a semiconductor, an interlayer insulating film, a liquid crystal alignment film, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a spectrum of 111 bis(carboxy)tricyclo[5,2,1,02'6]nonane. Figure 2 is a 13 (:11) spectrum of bis(carboxy)tricyclo[5,2,1,02'6]nonane. Figure 3 is a bis(gas carbonyl) tricyclic [5,2,1,02 '6] ^-NMR spectrum of decane. Figure 4 is a 13 (:氺1^11 spectrum of bis(gas carbonyl)tricyclo[5,2,1,02,6]nonane. Fig. 5 is a P-5 13C-NMR spectrum. Fig. 6 is a 13C-NMR spectrum of P-13. Fig. 7 is a 13C-NMR spectrum of P-14. Fig. 8 is a 13C-NMR spectrum of P-15. 136993.doc -117· 200940601 13C-NMR spectrum of 9 series P-16 Fig. 10 is a 13C-NMR spectrum of P-17. Fig. 11 is a 13C-NMR spectrum of P-19.

136993.doc -118-

Claims (1)

200940601 X. Patent application scope: 1. A resin structure: [Chemical 1] It has a crucible represented by the following general formula (1) in the molecule - HN-Xi-nh_c„Zi-C-OH (1) { Wherein 'X! represents a tetravalent organic group which does not contain a halogen atom, and H1 represents a divalent organic group represented by the following formula (2): [Chemical 2] (wherein 'L!, L2 and L3 each independently represent a hydrogen atom or a methyl group, and represent a hydrogen atom, a methyl group or a trans group). _ 2- A resin having a structure represented by the following formula (3) in the molecule: Ό 136993.doc 200940601 [Chemical 3] In the formula, X, &amp; X2 represents a tetravalent organic group which does not contain a halogen atom, and may be the same or different, and Z! represents a divalent organic group represented by the following general formula (2): [Chemical 4] L · (wherein, Li, L2 and L3 each independently represent a hydrogen atom or a methyl group, and L4 represents a hydrogen atom, a fluorenyl group or a hydroxyl group), and Z2 represents a divalent organic group having a halogen ring of 136993.doc 200940601 atom having an aromatic ring, Mi represents an integer of 1 to 200, X3 represents a 2 to 4-valent organic group which does not contain a halogen atom, and Z3 represents a tetravalent organic group which does not contain a halogen atom. m2 and ms each independently represent an integer of 〇~200, and m3 represents 〇~ An integer of 2, nu is an integer of 0 to 1, and the order of the units called, called, and called is not limited}. 3_ A resin according to claim 1 or 2, which has a structure represented by the following formula (4): [Chemical 5] ❹ Ο II C- = is independently selected from the group consisting of a gas atom, a carbon number group, and a substituted benzene ring, and the (4) R2 can be linked, and the heart and the organic group of the soil 1 }. ^Atom or carbon number is the resin of claim 1 or 2, which has the structure: the formula represented by the following formula (5). (5) 结 The knot represented by 136993.doc 200940601 Structure: [Chem. 7] A (6> indicates the knot of [Chemical 8] 7. The resin according to claim 1 or 2, which has a structure represented by the following formula (8): '° © [Chemical 9] Construction: 136993.doc -4- 200940601 [化 l〇] [化11] {In the formula, 10. As requested, L (10) R is a one-valent organic group having a carbon number of 1 to 4. The resin of item 1 or 2, which has a knot represented by the formula (11) of -P F [Chemical 12] 〇 [Chem. 13] (12) 136 136993.doc 200940601 12. The resin according to claim 1 or 2, which has a structure represented by the following formula (13): [Chem. 14] (13). 13. The resin according to claim 2, wherein the oxime 2 in the above formula (3) is at least one selected from the group consisting of the following structural formula (14): [Chem. 15] Ο {wherein' Ls is selected from the following monovalent groups of organic groups: [Chem. 16] (wherein 'L6 represents a carbon number is a valence alkyl group)}. 14. The resin according to claim 2, wherein the polyiminoimine group-containing unit portion in the above formula (3) has a group selected from the group consisting of the following formula (15) and the following formula (16); At least 1 structure: 136993.doc 200940601 [Chem. 17] Ν o=c, \J=o (16) The resin according to claim 1 or 2, wherein the end of the resin is at least one terminal group selected from the group consisting of the following structures: [Chem. 18] ❹ 16. A positive-type photosensitive resin composition having 1 to 100 parts by mass relative to the amount of the yttrium-based resin (including the solvent-soluble resin of the resin according to any one of claims 1 to 15) (Β) Photosensitive diazonaphthoquinone compound 17. The positive photosensitive resin composition of claim 16, which further comprises 100 to 2000 parts by mass of the (c) organic solvent. 18. If the request is 16 or 17 The positive photosensitive resin composition, wherein the sensory diazonaphthoquinone compound is selected from 1,2-naphthoquinonediazide-4-sulfonic acid which is a hydroxy compound represented by the following formula (17). The ester and the compound of the 1,2-naphthoquinonediazide-5-sulfonate of the compound 136993.doc 200940601 are one less compound: [Chem. 19] ❹ (17). 19. The positive photosensitive resin composition of claim 17, wherein (C) the organic solvent is 丫-butyl vinegar Q 20. The positive photosensitive resin composition of claim 16 or 17, which further contains 0.01~ 20 parts by mass of the (D) alkoxydecane compound. 21. The positive photosensitive resin composition of claim 20, wherein the (D) alkoxy oxime compound is at least selected from the group consisting of compounds represented by the following general formulae (18) to (25). A compound: [Chemical 20] i? S ? (x3)s H〇-c-x "C-N_X24j_(0-secret (18) (wherein the heart and another 2 represent a divalent organic group, χ3 and χ4 Represents a monovalent organic group 'and s represents an integer of 〇~2}; 136993.doc (19) 200940601 [Chem. 21] (Χ5), Η ο (^-owsi-Xr-Nc^ yCoon HOOC^ 'C-N- X9-S1—(O—Xn)3-s 〇H (X,〇)s { wherein, X7 and X9 represent a divalent organic group, X8 represents a tetravalent organic group, and X5, X6, XlG and X11 represent a monovalent group. Organic base, and S represents an integer from 0 to 2}; [Chem. 22] 4_NH—X丨3—Si—(Ο—X] 5)3^ (X14)s (2 0) wherein X13 represents a divalent organic group, X12, X14 and X15 represent a monovalent organic group, and s represents 0. An integer of ~2, and t represents an integer from 0 to 5}; [Chem. 23] Ο Η Xl6—C—N—Xj7—Si—(OX)9)3-8 ( 2 1 ) (Xl8)S {wherein Xl6 is not -NH-R20 or _0-R21 (here, R20 and Κ·2 1 is a monovalent organic group having no COOH group, and represents a divalent organic group, and 丨8 and 19 represent a monovalent organic group, and s represents an integer of 0 to 2; [Chem. 24] HS— X22—Sj—(〇X24)3-S (X23)s (2 2) {wherein, x22 represents a divalent organic group, X23 and X24 represent a monovalent organic group, 136993.doc -9- 200940601 and s represents 0 An integer of ~2}; [Chemical 25] h2n-c-nh-x2S-Si-(OX27)3.s 〇(X26)s (2 3) {wherein, x25 represents a divalent organic group, and X26 and X27 represent a monovalent organic group, and s represents an integer of 0 to 2}; [Chem. 26] X29—X30—si—(OX32)3-S (X3l)s (2 4) wherein x28 represents a hydrogen atom or a methyl group, and X29 is selected from the group 2 of the following formula: [Chem. 27] 〇 〇—CH〗 1—S〇2—〇Π II 0-C-NH—C-NH— 0 II —NH—C—NH—-Ο—NH—C-0—-Ο Ο Ο II II • C — 0* — — C— ? '3 i? —c- —NH—C— cf3 ; X3Q represents a divalent organic group, X31&amp;X32 represents a monovalent organic group, and S represents 0 to 2 An integer, and U represents an integer from 1 to 3}; and [28] (2 5) \ — 7^~Χ33—Χ34—Si—(〇X36)3-S (X35)s {where, X33 and X34 represents a divalent organic group, X35 and X36 represent a monovalent organic 136993.doc -10-200940601 group, and s represents an integer of 0 to 2} » 22. The positive photosensitive resin composition of claim 16 or 17, It further contains 5 to 20 parts by mass of a compound which causes a crosslinking reaction by heat. 23. The positive photosensitive resin composition of claim 22, wherein the compound which causes thermal crosslinking reaction by heat is selected from the group consisting of an epoxy group, a methyl group, an alkoxymethyl group or an oxygen group. At least one of a group consisting of a cyclobutane group and a biguanide diyl quinone imine compound. 24. The positive photosensitive resin composition of claim 16 or 17, further comprising 1 to 30 parts by mass of the compound selected from the group consisting of (F) acrylate compound, methacrylate compound, allyl group-containing compound, and At least one of a group consisting of a compound of an oxy group and a phenyl ester compound. 25. The positive photosensitive resin composition of claim 16 or 17, which further contains 1 to 30 parts by mass of (G) an organic compound having a carboxyl group in the molecule. A method of forming a hardening undulation pattern, comprising: a coating step of applying a positive photosensitive resin composition according to any one of claims 1 to 25 to a substrate; an exposure step of exposing the layer, A developing step of eluting and removing the exposed portion by a developing solution, and a heating step of heating the obtained undulating pattern. 27. A semiconductor skirt having a hardened relief pattern obtained by a method of forming a % of a request. 28. A negative photosensitive resin composition comprising: _ part by mass of (a) 3 of a resin having a resin as claimed in any one of claims 1 to 15, and 0.5 to 30 parts by mass of (H) by irradiation A compound which generates an acid by active light and 5 to 50 parts by mass of (1) a compound which can be crosslinked by an action of an acid. The negative photosensitive resin composition of claim 28, wherein (1) the compound crosslinkable by the action of an acid is a compound having a fluorenyl group or an oxo group p group in the molecule. . 30. A method of forming a hardened relief pattern comprising: a coating step of applying a negative photosensitive resin composition as claimed in claim 29 or 29 to a substrate, an exposure step of exposing the layer, and an exposure after exposure Step 31. A developing step of eluting and removing the unexposed portion by the developing solution, and a heating step of heating the obtained undulating pattern. Method of Forming Claim 30 A semiconductor device having a hardened relief pattern as obtained. 136993.doc 12