TW201005008A - Heat-resistant resin precursor and photosensitive resin composition comprising the same - Google Patents

Abstract

Disclosed is a novel alkali-soluble resin which can be used in a photosensitive resin composition to impart high sensitivity to the composition, enables the formation of a pattern with a developing solution (an aqueous 2.38 wt% tetramethylammonium hydroxide solution) that is normally used in the process for producing a semiconductor device, and can be cured into a heat-resistant film having excellent mechanical strength, in other words, has a high glass transition temperature and enables a relief pattern to have excellent solubility in propylene glycol monomethyl ether after development. The alkali-soluble resin has, in its molecule, a structure represented by general formula (1) [wherein X1 represents a tetravalent organic group containing a halogen atom; Z1 represents a bivalent organic group represented by general formula (2) (wherein L1 or L1's and L2 or L2's independently represent a methyl group or a hydroxy group; and n1 and n2 independently represent an integer of 0 to 3); and m1 represents an integer of 1 to 200].

Description

201005008 * Lu Liu, the invention description: [Technical Field] The present invention relates to an alkali-soluble resin, and a positive or negative photosensitive resin composition comprising the soluble resin, which is used as an electron An insulating material for a component or a display element, and a relief pattern for forming a heat-resistant resin material used for a purification film, a buffer film, and an interlayer insulating film in a semiconductor device. [Prior Art] ® It is known that the use of a surface protective film or an interlayer insulating film for a semiconductor device is preferably a polyimide resin having excellent heat resistance, electrical properties, and mechanical properties. The polyimine resin used for such applications is usually provided in the form of a photosensitive polyimide intermediate precursor composition, which can be sequentially patterned by active light by coating it on a substrate such as a ruthenium wafer. Exposure, development, and thermal imidization treatment, and a heat-resistant resin film having a fine relief pattern is easily formed on the substrate. However, in the case of using the above-mentioned photosensitive polyimide intermediate composition, in the development step, it is necessary to use a large amount of an organic solvent as a developing solution, and the viewpoint of cost, safety, and attention to environmental problems in recent years are mentioned. In terms of rising prices, the industry is seeking countermeasures against organic solvents. Affected by this, various heat-resistant photosensitive resin materials which can be developed in a dilute aqueous alkali solution in the same manner as the photoresist have recently been proposed. Recently, it has been highlighted that it contains polyhydroxy decylamine which is soluble in a dilute aqueous alkali solution = polyphenyl benzoate (hereinafter referred to as "PBQ (pGlybenz Qxaz〇le)") precursor and photosensitive diazonaphthoquinone compound (below a photosensitive resin composition (hereinafter referred to as "PAC (photoactive component)) such as "NQD ' 141 〇 19.do, 201005008 diazonaphthoquinone derivative") (hereinafter referred to as "patent document"), It has been actually used. Further, as a heat-resistant photosensitive resin composition which can be developed in a dilute aqueous alkali solution, many combinations have been proposed and used: a combination of an alkali-soluble resin having a phenolic hydroxyl group introduced into a side chain and a PAC, and utilization in a skeleton. A combination of a polyamidiamine, a ruthenium precursor polymer and a pac, which is obtained by exchanging a polyamidene precursor unit and a PBO precursor unit with trimellitic acid. The alkali-soluble resin used in combination with pAC in the above-mentioned heat-resistant photosensitive resin composition is mainly a polyamine which has a phenolic hydroxyl group such as a polyimide precursor or a pB-ruthenium precursor. By introducing the phenolic hydroxyl group into the polymer skeleton, the exposed portion is dissolved in the dilute alkali aqueous solution during development, and the unexposed portion is inhibited by the interaction of the phenolic hydroxyl group and the PAC to form a positive type. Embossed pattern. As a method for introducing a desired permeation group in a polymer, an aromatic diamine having an ortho-group and a phenolic hydroxyl group (hereinafter, also referred to as "dif. diamine") is generally used as a polyfluorene. A method of dehydrating condensation with (iv) a raw material of an amine. ☆ In the case where the acidity of the base of the desired diamine is low, the polyamine is insoluble in the rare aqueous solution, and the exposed portion is dissolved or left undeveloped at the time of development. On the other hand, when the acidity of the hydroxyl group of the phenolic diamine is lower than that of n, the interaction with the PAC is weak, so that the unexposed portion is also dissolved during development, and a high-quality relief pattern cannot be obtained. In the exposure step, the reduction projection projection (four) called the t-line stepper using the i-line of the mercury lamp is mainly used. This stepping 141019.doc 201005008 is a very expensive machine, so if the photosensitive resin composition is low in sensitivity, the exposure time required to form the relief pattern is prolonged, and the number of stepping machines required is increased. Lead to high cost of exposure process. Therefore, the industry strongly demands to increase the photosensitivity of the photosensitive resin composition. In the positive photosensitive resin composition, in order to improve the photosensitivity, it is first necessary to increase the i-line permeability of the polymer without impeding the decomposition of pAC in the exposed portion. Therefore, for the polymer used in the positive photosensitive resin composition, a line penetration property is required. 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 in the alkali developing solution, and as a result, the photosensitivity is high. Therefore, for the polymer used in the positive-sensitive resin group and the substance, the interaction with the pAC is required to be strong. However, in recent years, as a solvent used for the heat-resistant photosensitive resin composition, there is a demand for a semiconductor manufacturing step such as a γ·butyrolactone intermediate solvent which is superior to a highly detectable one such as a methyl group (four). The inclination of the amine-based solvent is therefore required to be soluble in γ-butyrolactone for the polymer used in the positive-type photosensitive resin composition. As a dilute alkali developer used for forming a pattern by using a heat-resistant photosensitive resin composition, a 38% by weight aqueous solution of tetramethylammonium hydroxide is usually used in the semiconductor manufacturing step (hereinafter, also referred to as "2 38%" TMAH (tetramethyl ammonium hydr〇xide>Jc solution), so strong, J, required to be developed in 2 · 38 % of TMAH aqueous solution. Also, in the semiconductor manufacturing step, the substrate failed to be coated or developed needs to be impregnated Regeneration in an organic solvent. One of the organic solvents used at this time is propylene glycol monomethyl ether. Therefore, the solubility of the embossed pattern in the development of the propylene 141019.doc 201005008 alcohol monomethyl ether is also required. Further, in the manufacturing process of the semiconductor device, the wiring of the photosensitive composition for the protective film is formed with a wiring circuit or a terminal for external connection. Therefore, the surface is not uniform, and the photosensitive resin is affected by this. When the composition is applied to the dicing 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. When the photosensitive resin composition used for the protective film is changed in the film thickness of the coating, it is necessary to change the amount of exposure and development time required for pattern formation, and there is a margin for patterning processing when the film thickness changes. The problem of the narrowness of the degree (margin). The photosensitive resin composition having a wide film thickness when forming a pattern with the same exposure amount and the same development time is strongly required. PB used as a positive photosensitive resin composition. As a precursor, a positive photosensitive resin composition containing a bis(3.amino-4-yl)-based phenyl condensate and a m-acid condensate and a PAC (refer to Patent Document) is proposed. In the embodiment of the invention, the material is not semi-conductive (four) the aqueous solution of 2.38 / 〇 通常 通常 通常 通常 通常 ' ' ' ' ' ' ' 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 The intrinsic solubility of the polymer of the phenolic hydroxyl group of the amine group is carried out. The inventors of the present invention synthesized the 4, 4, _ 2 stupids described in Patent Document 2 as a dicarboxylic acid. Dicarboxylic acid and double (3· When the polycondensate of the group _4_Phenylphenyl) ruthenium is insoluble in γ-butyrolactone, the transparency to the i-line is high, and the interaction with pAc is low, so the photosensitivity is not sufficiently satisfied. The following Patent Document 3 discloses that the alicyclic dicarboxylic acid and the phenolic 141019.doc 201005008 amine are ruthenium precursors from the acid, and the second embodiment is preferably the second (four)'. There is no bismuth (3_Aminopyridyl phenyl) hexafluoropropanol, and the polycondensate of the garment-g is dissolved in the Ν·methyl hydrazine (IV) sensitized _lipid composition. When the present inventors confirmed the sensitivity of the positive photosensitive resin composition, the glass transition temperature of the heat-resistant ruthenium film after curing was fine. The lower temperature of c. In addition, as an aliphatic dibasic acid or an alicyclic dibasic acid

The precursor of the invention is disclosed in the following Patent Documents 4 to 7, but it is considered that the photosensitive resin composition is not highly achievable, and the photosensitive resin composition is highly sensitive to form a pattern with the exposure amount and the same development time. In the case of a polymer having a wide film thickness margin. Patent Document 8 of the following discloses a heat-resistant polyamine having a helium gas having a tricyclo[5,2,1,〇]decane structure. A gas barrier film comprising a polybenzofluorene resin is disclosed in Patent Document 9 below. The following Patent Document 1 discloses a negative photosensitive resin composition comprising a ?-precursor resin and a compound which generates an acid by irradiation with radiation and a compound which can crosslink the resin by an action of an acid. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide an alkali-soluble resin which is patterned by the same exposure amount and the same development time when a photosensitive resin composition is prepared. In the case of a film having a wide film thickness and high sensitivity, a developing solution (2 38% by weight aqueous solution of tetramethylammonium hydroxide) generally used in the manufacturing steps of a semiconductor device can be used to form a pattern, which is soluble in γ_. Ding After the lactone solvent is cured, the mechanical strength of the heat-generating film is excellent, that is, the glass transition temperature is relatively excellent. The embossed pattern is excellent in solubility in propylene glycol monomethyl ether after development. Further, a method of forming a hardened relief pattern on a substrate using the composition, and a semiconductor device having the cured relief pattern are also to be solved by the present invention. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have reported that a phenolic hydroxyl group-containing polydecylamine (ρΒο precursor) derived from a dehydrated condensate of a phenolic diamine and an aromatic monocarboxylic acid is used. Study hard and repeat the experiment. It was found that the resin with a specific skeleton is soluble in γ-butyrolactone, and the transparency of the i-line of the mercury lamp is high. The interaction with the PAC is also strong, and the sensitivity is π, and the embossed pattern on the propylene glycol can be obtained after development. In the mercapto ether, the 'columnability is excellent, the same amount of exposure, the same amount of development time and the development time are formed. 141019.doc 201005008 A positive photosensitive resin composition having a wide film thickness margin. The study was conducted on a positive photosensitive resin composition using the cold-testable resin. *13 Further, 'the compound which can generate an acid by irradiation with radiation and the compound which crosslinks the resin by the acid 4 are combined with the resin of the present invention and studied. The result is that the material is required to be charged (4) New Resin The composition thus completes the invention. That is, the present invention is as follows. [1] An alkali-soluble resin having a structure represented by the following formula (1) in a molecule: [Chemical Formula 1] OH 〇 • ΝΗ-Χ, -ΝΗ-Ο-Ζ, -ϋ-ΟΗ

(1) (wherein, X represents a 4-valent organic group containing a halogen atom, and & represents a divalent organic group represented by the following formula (2), ❹ [Chemical 2]

(2) (In the case where L] and L2 have a plurality of cases, each of them is independently methyl or hydroxy, and ni and h represent an integer of 〇~3, and is an integer representing 〇〇2〇〇. [2] The alkali-soluble resin according to the above [], which has a structure represented by the following formula (3) in a molecule: 141019.doc -9- 201005008 [Chemical 3]

In the formula, X represents a tetravalent organic group containing a halogen atom, χ2 represents a tetravalent organic group not containing a functional atom, and Z1 represents a divalent organic group represented by the above formula (2). , Z2 represents a divalent organic group having a carbon number of 3 to 40, mi represents an integer of ^00, and Π12, m3, and Hi4 each independently represent an integer of 〇~2〇〇, where (η^+π^ When +π^+π!4) is set to 1〇〇%, the molar ratio is 11^/0, +1112 + 1113 + 1114) is 25% or more}. [3] The alkali-soluble resin according to the above [1] or [2], wherein X1 described in the formula (1) or (3) is the following structure: [Chemical 4]

[4] The alkali-soluble resin according to [2] above, wherein the oxime 2 described in the formula (3) is the following structure: [Chemical 5] CHj

[5] The alkali-soluble resin according to any one of the above [2] to [4] wherein the &> described in the general formula (3) is selected from the group consisting of the following structural formula (4) : 141019.doc 201005008 [Chem. 6]

In the formula, L5 is selected from the monovalent group of the following structural formula (5): [Chemical 7]

(wherein, L6 represents a monovalent alkyl group having a carbon number of 1 to 4)}. [6] The alkali-soluble resin according to any one of the above [1] to [5] wherein the formula (1) or the formula (3) has at least one selected from the group consisting of the following structural formula (6) A terminal group: [Chemical 8]

(6) [7] A positive-type photosensitive resin composition comprising (A) an alkali-soluble resin of the alkali-soluble resin according to any one of the above (1) to [6] A photosensitive diazonaphthoquinone compound containing 丨~丨 (8) parts by mass. [14] The positive photosensitive resin composition of the above [7], which further contains 100 to 2000 parts by mass of the (C) organic solvent. [9] The positive photosensitive resin composition according to the above [7] or [8] wherein (B) the photosensitive diazonaphthoquinone compound is selected from the group consisting of a polybasic compound represented by the following formula: - a group consisting of naphthalene diterpene nitrogen-4-carboxylate and 1,2 - awake · azide-5 - continuous acid vinegar of the succulent compound: [Chem. 9]

(7) The positive photosensitive resin composition of the above [8], wherein (c) the organic solvent is γ-butyrolactone. [11] The positive photosensitive substrate of any one of the above [7] to [1], which further comprises 0.01 to 20 parts by mass of the (D) alkoxydecane compound. [12] The positive photosensitive resin composition of the above [π], wherein the (D) alkoxydecane compound is selected from the group consisting of compounds represented by the following formula: (丨5): 10] xHX上上心(4) {wherein, XJX2 represents a divalent organic group, ΧΑΧ4 represents an organic eight 141019.doc -12· 201005008 and S represents an integer of 0~2}; [Chemical 11] (X5)s Η Ο

-O^-Si-XT-N-C^ yCOOH HOOC^ C—N—X^-Si—(O—Xjtb-s

O (9) {wherein, X7 and X9 represent a divalent organic group, X8 represents a tetravalent organic group, X5, X6, X丨ο and Χπ represent a monovalent organic group, and s represents an integer of 0 to 2}; 12]

In the formula, X13 represents a divalent organic group, X12, X14&X15 represents a monovalent organic group, s represents an integer of 0-2, and t represents an integer of 0-5; [Chem. 13]

Ο Η II IX\S-C—Ν—X| 7~Si—如如, (1 1) { where X!6 denotes -NH-R20 or -0-R21 (here, R20, and Κ·21 It represents a monovalent organic group which does not contain a COOH group, X17 represents a divalent organic group, χ18&19 represents a monovalent organic group, and s represents an integer of 0 to 2}; [Chem. 14] (1 2) HS-X22- Si—(0X24)3-* (%23k {wherein, X22 represents a divalent organic group 'X23 and X24 represent a monovalent organic group, and s represents an integer of 0 to 2}; 141019.doc -13- 201005008 15] H2N-C-NH-X23-S^-(〇X27)js ° 匕26, (1 3) {wherein X25 represents a divalent organic group' Xu and Xu represent a monovalent organic group, and s An integer representing 0 to 2}; '[Chemistry 16]

In the formula, Xu represents a hydrogen atom or a methyl group, and Xu represents a 2-valent group selected from the group of the following formula: 1 of 2 [Chem. 17]

"^CH〗One SOj. Ο U NH—C—NH^— ' O ·0· 〇0 •O C C,NH—C—NH-O 〇it n ——NH-C-0-- c——C—o— mC— I CFj

0 II •NH-O , X3〇 represents a divalent organic group, Xsi&X32 represents a valence organic group, s represents an integer ′ of 〇~2 and u represents an integer of 1 to 3};

NW^*X33~ X34—(〇X}«)3.S (15) {wherein, X33 is the same as X29 defined in the general formula (14), χ34 represents a divalent organic group, and Xu and X36 represent ^Jia Organic group, and s represents an integer of 〇~2}. [13] The positive photosensitive resin composition of any one of the above [7] to [12], 141,019.doc -14 to 201005008, which is subjected to a crosslinking reaction by heat, which further contains 0.5 to 50 parts by mass (e ) borrowed compounds. [14] The positive photosensitive resin composition according to the above [13], wherein (8) the compound which undergoes thermal crosslinking reaction by heat is selected from the group consisting of an epoxy group, a methyl group, an alkoxymethyl group or an epoxy group. a group consisting of a butyl compound and a bis-propyl naliamine compound. [15] The positive photosensitive resin composition of the above-mentioned [7] to [14], which is a positive photosensitive resin composition of the present invention, further comprising 0.5 to 50 parts by mass of ώ丄 ώ丄 ΐ ΐ (F) is selected from the group consisting of acrylates

At least one compound selected from the group consisting of a methacrylate compound, an allyl group-containing compound, a methoxy group-containing compound, and a phenyl ester compound. [16] The positive photosensitive resin composition according to any one of the above [7] to [15] further comprising 1 to 30 parts by mass of an organic compound having a carboxyl group in the molecule. a method of forming a hardened relief pattern, comprising: a coating step, the photosensitive resin composition according to any one of the above [7] to [16] being formed on a substrate in the form of a coating layer; an exposure step Exposing the layer; developing a step of eluting the exposed portion in the developing solution; and heating the substrate to heat the obtained relief pattern. [18] A semiconductor device having the above [17] A hardened relief pattern obtained by the formation method [19] A negative photosensitive resin composition comprising ruthenium by mass (Α) as in the above [1] to [6] Any of the alkali-soluble resins, 〇5~3〇 parts by mass of (Η) compounds which can produce acid by irradiation of active light, and 3~5 enamel 141019.doc •15· 201005008 parts (i) A compound which is crosslinked by the action of an acid. [20] The negative photosensitive resin composition of the above [19], wherein The compound is a compound having a methylol group or an alkoxymethyl group in the molecule. [21] A method for forming a hardened relief pattern, comprising: a coating step of: a negative photosensitive resin as described in [19] above The composition is coated on the substrate, the exposure step 'exposures the layer; the step of heating after exposure; the developing step 'dissolves the unexposed portion by the developing solution; and the heating step' performs the obtained relief pattern [22] A semiconductor device having a hardened relief pattern obtained by the method of forming a parameter as described in [21] above. [Effect of the Invention] According to the present invention, an alkali-soluble resin can be provided. When the photosensitive resin composition is formed, when the pattern is formed with the same exposure amount and the same development time, the film thickness margin is wide, and the sensitivity is high, and the developer which is generally used in the manufacturing process of the semiconductor device can be used. (2 38 weight 0 / 〇 tetramethylammonium hydroxide aqueous solution) formed a pattern, soluble in 丫 - butyrolactone solvent, the mechanical strength of the heat-resistant film after curing is excellent, that is, glass transfer temperature The higher development ❿ back relief pattern is excellent in solubility in propylene glycol monomethyl ether. Further, according to the present invention, there is also provided a method of forming a hardened relief pattern on a substrate using the composition, and having the hardened relief In the following, the resin (a) of the present invention is described below. The resin (a) of the present invention is a resin having a structure described in the following formula (1) in the molecule. It is preferred that the structure of the following formula (1) is a repeating unit. 141019.doc -16- 201005008 [Chem. 19]

OH 〇〇NH~XrNH—C—Z|-C- ΟΗ (1) {wherein Χι denotes a tetravalent organic group containing a dentate atom, and ^ represents a divalent organic group represented by the following formula (2), and Called the integer representing Bu 2} [化20]

(In the formula, when 复 and ]^2 are plural, each represents a methyl group or a hydroxyl group, and ~ and !^ represent an integer of 〇~3). As X1 in the above formula (1), for example, the following structure can be mentioned. [Chem. 21]

The X in the above formula (1) is preferably the following structure from the viewpoint of the photosensitivity in the case of producing a photosensitive resin composition. 141019.doc •17· 201005008 [Chem. 22]

In the above formula ^), ^ ^ # 1 is an organic group represented by the above formula (2), and from the viewpoint of the photosensitivity when the compound is free, it is preferred that the structure is [Chemical 23] a structural formula in the group consisting of formula (4).

The structural formula (a) is described. [Chem. 24] :a)

Further, in order to increase the mechanical properties of the heat-resistant film after curing, and to reduce the concentration of the halogen atom of the halogen atom, the structure of the alkali-soluble resin may have a structure of the following general formula. [Formula 25] In the formula, the 'X! table does not contain a tetravalent organic group having a carbon atom of 6 to 3 fluorene, and the watch does not contain a tetravalent organic group having a carbon number of 6 to 4 Å. , 匕 is not a divalent organic group represented by the above formula (2), & represents a carbon number of 3 to 40 2 © valence organic group ' mi represents an integer of l, called, called, and called respectively整数200 integer, here, when (mi+m2+m3+m4) is set to 100% moon shape, the molar ratio is called / (called +叱+1113+1114) is 25% or more}; In the formula (3), examples of & [Chem. 26]

141019.doc -19· 201005008

Among these, the following structural formula is particularly preferable from the viewpoint of the photosensitivity at the time of producing the photosensitive resin composition. [化27]

As Z2, for example, the following structural formula can be cited.

X)

141019.doc -20- 201005008

In the above formula, the above-mentioned structure is particularly preferable in terms of photosensitivity of photosensitivity when the photosensitive resin composition is prepared. Structural formula. In the above formula (3), mi represents an integer of from 1 to 200. M2, called and called respectively represent an integer of 〇~200. Mi, claw 2, and called can be block or random, respectively. In the case where it is set to 1%, the molar ratio is preferably 25% or more, more preferably 5% or more, more preferably 1 from the viewpoint of the photosensitivity of the composition. 〇〇%. The solvent-soluble resin ‘ having the structure described in the above formula (1) in the molecule has a structure of X, and can be synthesized by polycondensation of a di-m-acid having a phenolic hydroxyl group and a structure of =0. The solubility-soluble resin having a structure described in M3) in the molecule can be obtained by a diamine having a phenolic hydroxyl group having a structure of 141019.doc -21 - 201005008, and a structure having x2 as needed. The diamine having a phenolic hydroxyl group is synthesized by polycondensation with a dicarboxylic acid having a structure of Zi and, if necessary, a retardation of a structure having Z2. The synthesis methods of the above formulas (1) and (3) will be described in detail below. The second oxic acid having the structure of Z 1 can be obtained, for example, by the following method. As a raw material of the compound, bis(carboxy)tricyclo[5,2,1,02,6]decane is a tricyclo(5,2,1,decane)decanedioxol (manufactured by Tokyo Chemical Industry Co., Ltd.). Catalog No. T0850) is dissolved in acetonitrile or the like, and added 2 2 6,6-tetramethylpiperidinyloxy (hereinafter, also referred to as "TEMPO, 2,2,6,6-tetramethylpiperidine-l-〇xyl"), etc. The catalyst "is adjusted to a neutral pH by using sodium hydrogen phosphate, sodium dihydrogen phosphate, etc., while adding sodium sulfite and sodium disulfite to oxidize and purifying it. Compound bis (rebel) bicyclo[5,2,1,02'6] smoldering. Further, in addition to the above-described synthesis method, the synthesis method of Production Example A of Japanese Patent Laid-Open Publication No. SHO 58-119-538, or the synthesis method of Example 1 of Japanese Patent Laid-Open Publication No. 2002-504891, or The synthesis method of Synthesis Example 2 of H09-15846 was carried out. Further, among the compounds represented by the above compound group (a), a compound other than the compound having a bis(carboxy)tricyclo[5,2,1,〇2'6]nonane structure is a nonylcyclopentadiene compound. Dimer (Tokyo Chemical Industry Manufacturing Catalogue Νο·Μ0920), 1-methyldicyclopentadiene (Tokyo Chemical Industry Manufacturing Catalog No. M0910), 1-hydroxydicyclopentadiene (Tokyo Chemical Industry Manufacturing Catalog No.) H0684) as a raw material, after adding hydrogen bromide or hydrogenating hydrogen to the unsaturated bond of the above raw material by a method known from J. 〇rg. Chem., 45, 3527 (1980), according to J. Am Chem. Soc., 95, 249 (1973) known methods, in turn 141019.doc • 22- 201005008 Addition of carbon monoxide, water 'by introducing into the tricyclo[5,2,1,02'6]nonane skeleton 2 hydroxymethyl groups. As a method of synthesizing a dihydroxymethyl group, in addition to the above, a 9-boron bicyclic ring can be added to an unsaturated bond by a method known from J. Am. Chem. Soc., 91, 2150 (1969). After 3,1) decane is formed into an intermediate, it is reacted with carbon monoxide, and then reduced by LiAlH(OCH3)3 to produce a di-based fluorene matrix. For the di-based methyl group thus obtained, the dihydroxymethyl group can be similarly oxidized according to the method described in the case of obtaining bis(carboxy)tricyclo[5,2,1,02'6]nonane. This is the second of the goals. In addition to the above-described dicarboxylic acid having a structure of Zi, in order to achieve improvement in mechanical properties such as improvement in mechanical elongation or increase in glass transition temperature, it may be carried out with a dicarboxylic acid having a structure of 2; 2 other than the above dicarboxylic acid. Copolymerization. The dicarboxylic acid is preferably selected from the group consisting of an aromatic dicarboxylic acid having a carbon number of 8 to 36, an aliphatic dicarboxylic acid having a carbon number of 6 to 34, and an alicyclic dicarboxylic acid. At least one compound. Specifically, it may, for example, be isophthalic acid, p-dicarboxylic acid, 4,4,-diphenyl phthalic acid, 3,4, bisbiphthalic acid, 3,3, _diphenyl phthalic acid, 1 , 4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4,-sulfonyl bismuthic acid, 3 , 4'-sulfonyl bisbenzoic acid, 3,3'-cansyl bisbenzoic acid, 4,4'-diphenyl mystery dicarboxylic acid, 3,4'-diphenyl ether dicarboxylic acid, 3,3, Diphenyl ether dicarboxylic acid, 2,2-bis(4·carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)propane, 22,_dimethyl-44,·diphenyl , 3,3'-dimethyl-4,4,-diphenyl phthalate, 2,2, dimethyl _3,3,-diphenyl phthalate, 9,9-bis (4-(4- Carboxyphenoxy)phenyl)anthracene, 9,9-bis(4-(3-carboxyphenoxy)phenyl)purine, 4,4.-bis(4-carboxyphenoxy)biphenyl, 4, 4,-bis(3-carboxy 141019.doc -23- 201005008 phenoxy)biphenyl, 3,4'-bis(4-carboxyphenoxy)biphenyl, 3,4,_bis (3_竣Phenyloxy)biphenyl, 3,3,-bis(4-carboxyphenoxy)biphenyl, 3,3,_bis(3-sulfophenoxy)biphenyl, 4,4'-bis ( 4-carboxyphenoxy P-triphenyl, 4,4,_bis(4-carboxyphenoxy) m-triphenyl, 3,4'-bis(4-carboxyphenoxy)-p-triphenyl, 33,_bis(4.carboxybenzene Oxyl) p-triphenyl, 3,4,-bis(4-carboxyphenoxy) m-triphenyl, 3,3'-bis(4-carboxyphenoxy) m-triphenyl, 4,4,-bis ( 3-carboxyphenoxy)p-triphenyl, 4,4i-bis(3-carboxyphenoxy) m-triphenyl, 3,4,_bis(3-carboxyphenoxy)-p-diphenyl, 3,3' - bis(3-carboxyphenoxy)-p-triphenyl, 34,-bis(3carboxyphenoxy) m-triphenyl, 3,3,-bis(3-carboxyphenoxy) m-triphenyl, M• ring Succinic acid, 1,4-cyclohexanedidecanoic acid, iota, 2_cyclohexanedicarboxylic acid, 4,4, dibenzoquinone dicarboxylic acid, 1,3-benzenediacetic acid, iota-4-benzenediacetic acid , Honghong adamantane dicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, phthalic acid, azelaic acid, International Publication No. 5/〇68535 5-amino-isophthalic acid derivatives such as those contained in the manual. In the case of the photosensitive resin composition, it is preferred that the oxime 2 has the following general formula in terms of solubility in a solution in a dilute aqueous alkali solution. 4) The structure of the representation. [化30]

make. In the formula, L5 is selected from the following structural formula (7). 141019.doc (4) 201005008 [Chem. 31]

(In the formula, "an alkylene group having a carbon number of 1 to 4") When the alkali-soluble resin is produced, the above-mentioned dicarboxylic acid may be used singly or in combination of two or more kinds. Ο

Further, as the dicarboxylic acid, the following dicarboxylic acid-containing dicarboxylic acid can be used as the copolymerization. The acid-containing catalyst is a catalyst such as ruthenium, and the tetras-acid di Sf and the carbon compound having a carbon number of 丨 are used as an organic solvent. Obtained by carrying out the reaction. Examples of such tetracarboxylic acids are described below. Examples of the alcohol compound having 1 to 2 carbon atoms include yeast, isopropanol, butanol, tert-butanol, pentanol, and methyl. Methanol, ethanol, hydroxyethyl propyl acrylate, for example, using a bis(smoothyl)tricyclo[^(^癸院与芳香二叛酸2 is a dicarboxylic acid, and for example, a phenolic diamine will be used for 2,2_double When (3_amino-4-ylhydroxyphenyl)propane is calcined with 2,2-bis(3.amino-4-yl-phenylene)hexafluoro(tetra) as a diamine having a diphenolic hydroxyl group When the following method is used, the i-line permeability of the alkali-soluble resin is better in sensitivity: first, 2,2-biguanide-amino-4-hydroxyphenyl)hexafluoropropane and bis(carboxy)tricyclo[ My6]decane, condensation' followed by addition of 2,2-bis(3-amino-4-pyridyl)propylamine, addition of an aromatic dicarboxylic acid, and a polycondensation block copolymerization process. The copolymerization ratio of the dicarboxylic acid component containing Z1 and the dicarboxylic acid component containing Z2 can be arbitrarily selected to increase the photosensitivity of the composition, and the polycondensate is 141019.doc •25-201005008 γ-butyrolactone solvent In terms of solubility, it is preferred that the bismuth-containing retinoid component accounts for 30 mol% or more of the total dicarboxylic acid component, more preferably 5 〇 mol% or more, and the photosensitivity of the composition is considered. More preferably, the dicarboxylic acid used in the synthesis of the alkali-soluble resin may be used in the state of helium using sulfene gas. Specific examples of the synthesis method of helium include dicarboxylic acid and excess sulfoxide in the presence of a catalyst such as N,N-dimethylformamide, pyridine or vaporized benzyltriethylamine. The gas reaction is obtained by distilling off excess sulfoxide by heating and depressurizing, and the helium gas can be obtained by recrystallizing the residue of the reaction liquid by using a solvent such as hexane or toluene. Further, it may be used for the polymerization of an alkali-soluble resin without purification. Further, a catalyst may be used which is prepared by using a dehydrating condensing agent such as dicyclohexylcarbodiimide to dicarboxylic acid and N-hydroxybenzotriazole (hereinafter also referred to as HOBT 'hydroxy benzotriazole". Catalyst for HOBT active esters. The diamine component having a phenolic hydroxyl group which is used for the synthesis of the alkali-soluble resin of the present invention may, for example, be 2,2-bis(3amino-4-hydroxyphenyl)hexafluoropropane, 2 , 2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-mono(difluoroindolyl)-3,3'-dihydroxy-4,4,-diaminobiphenyl, 2,2'-bis(difluoromethyl)-3,3·-diamino-4,4,-dihydroxybiphenyl, 2-trifluoromethyl_3,5-monoamino-1,4- Dihydroxybenzene, 2,6-bis(trifluoromethyl)_3,5-diamino]14. monohydroxybenzene. Among them, 2,2-bis(3-amino-4-ylhydroxyphenyl)hexafluoropropane is a preferable compound in terms of high photosensitivity. As a diamine component containing X2 having a desired hydroxyl group, '2,2-bis(3-amino-4-pyridyl)propane, 22 bis(4-amino)-3- can be preferably used. 141019.doc -26· 201005008 phenyl)propane, 3,5-diamino-1-hydroxybenzene, 4,6-diamino-u-di

Benzobenzene, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-dihydroxy-3,3,-diaminobiphenyl, 3,4-diyl-3 ^4'-Diaminobiphenyl, bis(3-amino-4-yl-phenylphenyl), bis(3-amino-4-ylphenyl) sulfide, bis(3-amino) 4-hydroxyphenyl)decane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)sulfone, 9,9-bis(4-amino-3) -hydroxyphenyl) 9,9,bis(3-amino-4-hydroxyphenyl), 1,1-bis(4-amino-3-hydroxyphenyl)cyclohexane, 1,1- Bis(3-amino-4-phenylphenyl)cyclohexane. The aged diamines may be used singly or in combination of two or more. Among the preferred compounds, 2,2 bis(3-amino-4-hydroxyphenyl)propane and bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino group) -4-Hydroxyphenyl)propane is more preferred because of the lightness of the resin composition. The copolymerization ratio of the diamine component having a phenolic hydroxyl group containing Xi to the diamine component having a phenolic hydroxyl group of & can be arbitrarily selected, and if a total amount of the diamine component containing < The polymerization ratio _ is used in the semiconductor manufacturing step to dissolve/dissolve in the edge cleaning (such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propyl acrylate, propylene glycol) used in the squeaking or secondary processing.醆甲童., 乳基甲 s曰4 solvent. If all the diamines used in the polycondensate, 6 匕 3 x 丨 of the phenolic hydroxyl group of the diamine component is 25 mol% or more, then ~ , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In all the solvents, as the diamine component of the dibasic thiol group containing X2, the bis(4) amine barrier is used because the acidity of the phenolic hydroxyl group is too high, I41019.doc 27-201005008 It is preferred to copolymerize with a diamine having no phenolic hydroxyl group or to use a slightly larger molecular weight Adjusting the concentration of the desired base. The concentration of the phenolic hydroxyl group in the alkali soluble resin of bis(4amino-3-hydroxyphenyl)sulfone is preferably 2.0 to 5.0 millimolar, more preferably 2.5~45 millimolar, more preferably 3.0~4·0 millimolar. When manufacturing an alkali-soluble resin, in addition to the above phenolic diamine, it is also possible to copolymerize a diamine which does not have a desired trans group ( Hereinafter, it is referred to as "non-promising monoamine", thereby controlling the solubility or physical properties in the aqueous solution. The non-diuretic diamine is a 2- to 4-valent organic group which does not contain a halogen atom, and preferably, it is not An aromatic diamine or a diamino polyoxyalkylene having a desired transposition number of 6 to 30. Specifically, as the non-phenolic diamine, 4, 4, (or 3, 4,_,3,3'-,2,4'-)diaminodiphenyl ether, 4,4'·(or 33,_)diaminodiphenyl, 4,4-(or 3 , 3-) monoaminodiphenylsulfonium, 4,4'-dibenyldiamine, 3,3,-dibenzophenone diamine, 4,4,-bis(4-aminophenoxyl) Phenyl sulfone, 44, bis(3-aminophenoxy)phenyl sulfone, 4,4'-bis(4-aminophenoxy) phenyl, U4-double ( 4-Amino-p-oxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis{4-(4-amino basic) ketone, propylene, 3,3 ',5,5'-tetramethyl-4,41-diaminodiphenyl decane, 2,2'-bis(4-aminophenyl)propane, 2,2,6,6,tetra Mercapto-4,4,-diaminobiphenyl, 2,2,6,6,tetrakis(trifluoromethyl)_4,4,-diaminobiphenyl, M-double {(4-amine Phenyl)-2-propyl}benzene, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(4-amine basic oxy-based) fluorene, 3,3'-dimethyl An aromatic diamine such as aniline, 3,3,dimethoxybenzidine or 3,5-diaminobenzoic acid, 2,6-diaminopyridine, 2,4-diaminopyridine, M _Bis(4-aminophenyl-2-propyl) 141019.doc -28· 201005008 Diamines such as benzene and monoamine polyoxyalkylene compounds. The non-phenolic diamine may be used singly or in combination of two or more. When the alkali-soluble resin of the present invention is actually synthesized, a phenolic diamine or a non-phenolic diamine may be dissolved in a suitable solvent such as N-methylpyrrolidone or N,N-dimethylacetamide, and pyridine is added. a tertiary amine such as triethylamine is used as a catalyst, and a compound obtained by chlorinating the above-mentioned carboxylic acid hydrazine is dissolved in a suitable solvent such as γ-butyrolactone or acetone, and then added dropwise to -30^~ In the above phenolic diamine or non-phenolic diamine solution of 151, the target polycondensation structure is thereby obtained. The soluble resin can be obtained without any problem even if only the above polybenzoxazole precursor unit is used. It can also be obtained by cyclizing and condensing a tetracarboxylic dianhydride with an aromatic diamine having a phenolic hydroxyl group as needed. The polyamidene unit having a phenolic hydroxyl group is copolymerized. The tetracarboxylic dianhydride in the case of the above polyimine unit is preferably an aromatic tetracarboxylic dianhydride having a number of from 8 to 36, and an alicyclic ring having a carbon number of 6 to 34. a compound in a few acid dianhydrides. A boat can be enumerated: 5_(2,5-dioxotetrahydro 3 furanylmethylcyclohexene oxime, dicarboxylic anhydride, benzoic acid 1'2'3, 4_ this four-acid di-hepatic, 2,3',4,4'-benzophenone tetracarboxylic acid two-needle, 2,2' 3 m - a guanidine tetracarboxylic dianhydride, 3,3',4,4-diphenyltetracarboxylic acid ' '斗'4 - 联二笨四tetracarboxylic acid liver, 3,3" bis-tetrabenzoic acid dioxin, 3,3"", 4,4' pentabenzenetetracarboxylic dianhydride, 2, 2,, 3, 3,·Bibenzoic acid, wild, methylene-4,4′·diphthalic dianhydride, 1,1-diethylene tert-butyl phthalate dianhydride, 2,2-propylene _4,4'·diphthalic anhydride 1'2·extended ethyl-4,4′-diphthalic acid dianhydride, 1,3-trientylene group _ o-m-formic acid dixan, 1, 4_tetramethylene-4,4'-di-o-p-dicarboxylic acid 141019.doc ,29· 201005008 dianhydride, 1,5-pentamethylene·4,4′-diphthalic acid dianhydride, Bis(3,4_bis-t-phenylphenyl)ether dianhydride, thio-4,4'-diphthalic dianhydride, cansyl _ 4,4·-diphthalic dianhydride, 13 -bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride l,4-bis(3,4-di-repentylphenoxy)-one-needle, 1,3-bis[2-(3,4-di-densylphenyl)-2-propyl]benzene two-pin, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene 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-dioxaphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethyl sulphide, two needles, 1 , 3 -bis(3,4-di-phenylidenephenyl)-1,1,3,3·tetramethyldioxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1, 2,5,8-naphthalenetetracarboxylic acid two-needle, 1,2,5,6-naphthalenetetracarboxylic acid di-hepatic, 3,4,9,10·quinonetetracarboxylic acid dioxane, 2,3,6,7 - 蒽tetracarboxylic dianhydride, 12,7,8-phenanthrenecarboxylic acid dianhydride, ethyltetracarboxylic dianhydride, 12,3,^ butane tetradecanoic acid, 1,2,3,4-cyclobutane Burning tetracarboxylic acid-hepatic, cyclopentalic acid tetracarboxylic dianhydride, cyclohexanol-1,2,3,4·tetracarboxylic acid-hepatic, cyclohexan-1,2,4,5-tetradecanoic acid dianhydride, 3 , 3',4,4'-dicyclohexyltetracarboxylic acid dihepatic, several groups _4,4, _ double (cyclohexinal - hydrazine, 2-dicarboxylic acid) dianhydride, methylene-4,4·-bis(cyclohexane-dicarboxylic acid) dianhydride, 1,2-extended ethyl-4,4'-bis (cyclohexene) -1,2-dicarboxylic acid) dianhydride, j, meethethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene _4,4,_ Bis(cyclohexane-1,2-didecanoic acid) dianhydride, oxy-4,4,-bis(cyclohexane 4,2 dicarboxylic acid) dianhydride, thio-4,4'-double (ring Hexane-1,2-dicarboxylic acid) dianhydride sulfonyl _44, bis (cyclohexane-1,2-didecanoic acid) dianhydride, bicyclo[2,2,2]oct-7-ene -2,3,5,6-tetracarboxylic dianhydride, ^1-[18,511,6 ft]-3-clear bicyclic [3,2,1] Xinxuan_2,4-di 141019.doc •30 · 201005008 Keto-6-spiro-3,-(tetrahydrofuran-2,5,_dione), 4_(2,5-dioxotetrahydrofuran_3_yl)-l'2,3,4-tetrahydronaphthalene_ 1,2-dicarboxylic anhydride, ethylene glycol bis(3,4-dicarboxylic anhydride phenyl) ether, etc., of which 5_(2,5-dioxotetrahydro-3·furanyl)3_A is preferred Cyclohexene-1,2-dicarboxylic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 4,4,_(4 , 4, _ isopropylidene diphenyloxy) bis(phthalic anhydride) ' Among them, from the viewpoint of the transparency of the ruthenium line of the mercury lamp, 5-(2,5-dioxotetrahydro_3_furanyl) is more preferable in terms of solubility and photosensitivity in an aqueous alkali solution. _3_Methylcyclohexene_丨, 2-dicarboxylic anhydride, bis(3,4-dicarboxyphenyl)ether dianhydride. The diamine having a phenolic hydroxyl group used in the synthesis of the quinone imine unit having a phenolic hydroxyl group is selected from the group of the above phenolic diamines. Wherein 2,2_bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-ylhydroxyphenyl)propane has higher photosensitivity Therefore, it is better. The dehydration condensation reaction in the synthesis of the above quinone imine unit can be carried out by heating the above tetracarboxylic dianhydride and the above phenolic diamine in an acid or base catalyst to a temperature of 30 ° C to 220 ° C, preferably It is carried out at 170 ° C to 20 (TC). As the acid catalyst, an inorganic acid such as sulfuric acid or an organic acid such as a silicic acid which is usually used for the production of polyiminoimine can be used. As the base catalyst, pyridine, triethylamine, dimethylaminopyridine, hydrazine, 8-diazabicyclo(5,4,0) 稀 _7, 1, may be used. 3,5,7-tetraazabicyclo (3,3,i,l,3,7)decane, triethylenediamine, etc. Further, in particular, the following method can be employed: without adding a polycondensation catalyst or the like The temperature of the reaction liquid is maintained at a temperature not higher than the temperature at which the hydrazine imidization reaction is carried out, and the water formed by the dehydration reaction is removed from the reaction system by using an azeotropic solvent such as toluene or the like to complete the hydrazine imidation. 141019.doc •31· 201005008 Combined reaction. As a reaction solvent for performing the dehydration condensation reaction, in addition to the solvent used to azeotrope the water, it is preferred to a polar organic solvent for dissolving an alkali-soluble resin soluble in an aqueous solution. As the polar solvent, γ-butyrolactone, N-methyl ketone, dimethylamine, and sulfhydryl can be used. Acetamide, tetramethyl gland, cyclobutyl or the like. In the production of the above polyimine unit, in addition to the above phenolic diamine, if necessary, the above-mentioned non-prone diamine can be gathered to control the aqueous solution. In the case of using two or more kinds of tetracarboxylic dianhydrides or two or more kinds of phenolic diamines or non-prone diamines, it may be a block copolymer using a sequential reaction. The condensate; when a raw material of three or more components is added, a raw material may be simultaneously added to the reaction system to prepare a random copolymer condensate. The soluble resin may be modified with the following terminal group as a modified end. The method can be used to synthesize a suitable amount of maleic anhydride, succinic anhydride, cinnamic anhydride, 5-norbornene anhydride, 4-ethynyl phthalic anhydride, phenylethynyl phthalate Anhydride, 3,6_ Q epoxy -1,2,3,6·tetrahydrophthalic anhydride, 4_cyclohexene", 2-dicarboxylic anhydride, cyclohexane-1,2-diphthalic anhydride, 4·methylcyclohexane_丨, 2 dicarboxylic anhydride, 4-aminostyrene, 4-ethynyl aniline, or 3-ethynyl aniline, etc. Among them, in order to improve the two mechanical elongation, or to increase the glass transition temperature, the ruthenium has a lower selected from the following At least one terminal group in the group consisting of the structural formula (6), and the dicarboxylic acid used in the present invention may be left as a terminal. 141019.doc -32· 201005008 [Chem. 32]

Odd; the weight average molecular weight of the alkali-soluble resin, the weight average molecular weight in terms of polystyrene is 3000 to 100000, the mechanical properties are improved when the molecular weight is 5000 or more, and the dispersion in 2.38% of the water core liquid when the molecular weight is 70,000 or less The solubility in propylene glycol methyl ether acetate is improved, and the analytical performance of the relief pattern is improved. The alkali-soluble resin produced can be used by separating and re-dissolving the alkali-soluble resin in an organic solvent through a purification step. The specific purification step is as follows. First, the soluble resin is precipitated by adding a poor solvent such as methanol or ethanol 'isopropyl alcohol or water' to the alkali-soluble resin solution obtained by the above-mentioned production method. Secondly, 're-dissolve it in γ·丁内 s or ν_methyl 咬 纲 等 & & 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄 胄. Finally, the dissolved droplets were added to pure water, and the precipitate was separated by filtration, followed by vacuum drying. Thereby, a low molecular weight component, an ionic impurity or the like can also be removed. <Positive Photosensitive Resin Composition> (Α) Tested Soluble Resin When the positive photosensitive resin composition is prepared, the resin of the present invention is contained. 0) 141019.doc •33· 201005008

The (A) alkali-soluble resin is an essential component. The alkali-soluble resin other than the resin (a) is, for example, an alkali-soluble resin or a precursor having at least one group selected from the group consisting of a phenolic hydroxyl group and a carboxyl group, and specifically, A phenol resin and a derivative thereof represented by a novolak resin or a resol resin, polyhydroxystyrene and a derivative thereof, a resin having a structure in which the resin is intramolecularly copolymerized, and a resin of the present invention ( a) a PBO precursor other than an alkali aqueous solution soluble polymer, a phenolic hydroxyl group-containing aqueous solution soluble polyimine, a tetramine-derived indole bond derived from a tetracarboxylic acid and a diamine Body and so on. In the present invention, in order to exhibit the desired effect, the ratio of the resin (&) of the present invention to the (A) alkali-soluble resin is preferably 1% by mass or more, more preferably 20% by mass or more, more preferably Good is 4% by mass or more. (B) Photosensitive diazonaphthoquinone compound The photosensitive diazo naphthalene compound (4) used in the production of a positive photosensitive resin composition (hereinafter also referred to as "the present composition") has a specific structure as described in detail below. U2 naphthalene brewing two stacks of gas based compounds

At least one compound of the group consisting of sulfonic acid vinegar and the polypyridyl compound in the group consisting of diazide _5_sulfonic acid vinegar (also referred to as "NQD compound of polyamino compound") . The NQD compound of the poly-based compound can be obtained by converting the naphthoquinone 4-nitrogen acid compound into a gas by using a (tetra) acid or a sulfurous gas, and then obtaining the hm gas and the multi-menu The base compound undergoes a condensation reaction. For example, _ 』 获得 is obtained by the following method: in the presence of dioxin L (tetra), etc. (d) t 'in the presence of an organic catalyst such as triethylamine 141019.doc • 34· 201005008, the polyhydroxy compound and 1 > 2_naphthoquinone The specific amount of nitrogen _5_sulfonium gas or 1,2-naphthoquinonediazide-4-sulfonyl chloride is reacted to carry out esterification, and the obtained product is washed with water and dried. Hereinafter, a photosensitive diazonaphthoquinone compound which is obtained by combining with the resin of the present invention to obtain a high-sensitivity and excellent embossing pattern without swelling is shown. 1. A NqD compound of a polyhydroxy compound represented by the following formula (B1) [Chem. 33]

(B1) k, 丨, m, and 11 each independently represent 1 or 2, each independently representing a group consisting of a hydrogen atom, a dentate atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group, and a fluorenyl group. The groups in the group, Υι~Υ3, respectively, are not selected from a single bond, _〇·, _s〇_, _s〇2_, _c〇_, _c〇2.

a group of a group consisting of an organic group represented by an organic group represented by the following formula: [Chem. 34]

(wherein, the ruler ^ and the Han! 2 each independently represent at least one monovalent group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, an allyl group, and a substituted allyl group) 141019.doc -35- 201005008 [化35]

-

Rl4 (wherein R13 to R16 each independently represent a hydrogen atom or an alkyl group, and W represents an integer of 1 to 5) [Chem. 36]

(In the formula, R17 to R20 each independently represent a hydrogen atom or an alkyl group.) The polyhydroxy group represented by [Chem. 18] to [Chem. 32] described in JP-A-2001-109149 NQD compound of the compound. The entire contents described in Japanese Laid-Open Patent Publication No. 2001-109149 are incorporated herein by reference. The following are NQD compounds of the following polyhydroxy compounds. [化37]

2. A NQD compound of a polyhydroxy compound represented by the following formula (B2) 141019.doc -36- 201005008 [Chem. 38]

(B 2)

w 〜 刀 别 independently represents an i-valent organic group, b represents 0 or 1 ' a, C, d, and e respectively represent an integer of 〇 〜 3, f, g, h, and i respectively represent an integer of 〇 〜 2 . In addition, the sum of [, LV, and ^ is 1 or more] [Chemical 39] As a specific compound, those represented by [Chem. 23] to [Chem. 28] described in Japanese Patent Laid-Open No. 38-A No. . The entire contents described in Japanese Laid-Open Patent Publication No. 2001-092138 are incorporated herein by reference. Among them, the NQD compound of the following polyhydroxy compound has a high sensitivity and a low precipitation property in the positive photosensitive resin composition, so that it is preferably 0 141019.doc -37- 201005008 [Chem. 40]

[化41]

[化42]

[化43]

3. NQD compound of a polyhydroxy compound represented by the following formula (B3) 141019.doc -38- 201005008 [Chem. 44]

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, and k T and k are independently represented The monovalent group in the group consisting of a hydrogen atom and a monovalent organic group is selected as a specific preferred example, and the method described in Japanese Laid-Open Patent Publication No. 2004-3 47902 can be cited. The compound represented by 25]. The entire contents described in Japanese Laid-Open Patent Publication No. 2004-347902 are incorporated herein by reference. (Incorporated By Reference) wherein the following NQD compounds of the polyhydroxy compound are highly sensitive to positive photosensitive The precipitation property in the resin composition is low, so that it is preferred. [化45]

In the formula, p is an integer from 0 to 9} 141019.doc -39- 201005008 4. The NQD compound of the polyhydroxy compound represented by the following formula (B4) [Chem. 46]

Wherein A represents an aliphatic divalent organic group containing a tertiary or quaternary carbon, and Μ represents at least one selected from the group represented by the following chemical formula: [Chem. 47]

Specific examples of the compound include compounds represented by [Chem. 22] to [Chem. 28] described in JP-A-2003-13 1368. The entire contents described in the Japanese Patent Laid-Open Publication No. 2003-13 1368 are incorporated herein by reference. Among them, the NQD compound of the following polyhydroxy compound is preferred because of its high sensitivity and low precipitation in the positive photosensitive resin composition. [化48]

141019.doc •40- 201005008 5. NQD compound of polyhydroxy compound represented by the following formula (B5) [Chem. 49]

In the formula, R25 represents a monovalent organic group represented by the following formula, and may be respectively the same or different, and q is independently an integer of 0 to 2} [Chem. 50]

(wherein R26 independently represents at least one monovalent organic group selected from the group consisting of an alkyl group and a cycloalkyl group, and r is each independently an integer of 0 to 2). As a specific compound, there is an NQD compound of a polyhydroxy compound represented by [Chem. 17] to [Chem. 22] described in Japanese Laid-Open Patent Publication No. 2004-109849. The entire contents described in Japanese Laid-Open Patent Publication No. 2004-109849 are incorporated herein by reference. (Incorporated By Reference) wherein the following NQD compounds of the polyhydroxy compound are highly sensitive and positively sensitive. The precipitation property in the resin composition is low, so it is preferably 0 141019.doc •41 - 201005008 [Chem. 51]

[化52]

6. A NQD compound of a polyhydroxy compound represented by the following formula (B6) 141019.doc • 42· 201005008 [Chem. 54]

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. As a specific compound, it is exemplified in Japanese Laid-Open Patent Publication No. 2001-356475. The compound represented by [Chem. 18] to [Chem. 22] is described. The entire contents described in the Japanese Patent Laid-Open Publication No. 2001-356475 are hereby incorporated by reference. Among them, the NQD compound of the following polyhydroxy compound is preferred because of its high sensitivity and low precipitation in the positive photosensitive resin composition. [化55]

7. A NQD compound of a polyhydroxy compound represented by the following formula (B7) [Chem. 56]

In the formula, a plurality of R28 independently represent a valence of 141019.doc -43-201005008 represented by the following formula, S independently represents an integer of 0 to 2, and R29 represents a hydrogen atom, an alkyl group or a ring. Alkyl}

(In the formula, each represents an alkyl group or a cycloalkyl group, and t each independently represents an integer of 0 to 2). As a specific compound, there is a method described in JP-A-2005-008626. An NQD compound of the polyhydroxy compound represented by 16]. The entire contents described in Japanese Patent Laid-Open Publication No. Hei No. 2005-008626 are incorporated herein by reference. (Incorporated By Reference) wherein the NQD compound of the following polybasic compound is highly sensitive and positive. The precipitation property in the photosensitive resin composition is low, which is preferable. [化58]

[化59]

141019.doc 44 - 201005008 In the photosensitive diazo naphthalene brewing compound, when the photosensitive resin composition is highly sensitive and has a pattern formed by the same exposure amount and the same development time, the film thickness margin is wide and the precipitation property is high. In the lower aspect, the most preferred are NQD compounds of the following polyhydroxy compounds. [60]

In the present composition, the naphthoquinonediazidesulfonyl group in the photosensitive diazonaphthoquinone compound can be preferably used in 5-naphthoquinonediazidesulfonyl or 4-naphthoquinonediazidesulfonate. Any of them. The 4-naphthoquinonediazidesulfonyl ester compound has an absorption peak in the i-line region of the mercury lamp and is suitable for i-line exposure. The absorption peak of the 5-naphthoquinonediazidesulfonyl ester compound is extended to the g-ray region of the mercury lamp, and is suitable for g-ray exposure. In the present invention, it is preferred to select a 4-naphthoquinonediazidesulfonyl ester compound or a 5-naphthoquinonediazidesulfonyl ester compound depending on the wavelength of exposure. Further, a naphthoquinonediazidesulfonyl ester compound having a 4-naphthoquinonediazidesulfonyl group or a 5-naphthoquinonediazidesulfonyl group may be obtained in the same molecule, and 4-naphthoquinone may also be used. The diazoxysulfonyl ester compound is used in combination with a 5-naphthoquinonediazidesulfonyl ester compound. In the present composition, the amount of the photosensitive diazonaphthoquinone compound to be added is 1 to 100 parts by mass, preferably 141019.doc -45 to 201005008, per 100 parts by mass of the (A) alkali-soluble resin. The amount of addition is 1 and the amount of addition is 100 to 3 parts by mass. It is more preferable that the sensitivity is increased when the mass is more than 1 to 3 parts by mass; on the other hand, the amount is not generated after exposure. Broken. (C) Organic solvent As the refrigerant for use in the production of the resin composition using the resin of the present invention, N-methyl·2_(tetra), Ν'Ν·dimethylethene, which is a polar solvent, may be mentioned. Amine, N,N-dimethylformamide, dimethyl sulfoxide, tetramethyl gland, γ-butyrolactone, and morphine. Further, in addition to the polar solvent, it may be mixed with a common organic solvent, a brew, an internal vinegar, an ether, a toothed hydrocarbon, or a hydrocarbon. For example, a residual, methyl ethyl ketone, or the like may be used. Methyl isobutyl, cyclohexanone, methyl acetate, acetic acid, B: vinegar: oxalic acid, diethyl lactic acid, lactic acid, lactic acid, lactic acid, butyl vinegar, propyl alcohol, early methyl ether Acid ester, propylene glycol monomethyl ether, benzyl alcohol, phenylethylene glycol, ethylene glycol dimethyl ether, [ethylene glycol dimethyl ether, tetrahydrofuran, -chloroform, alpha gas, monochloroprene Gas, benzene, ortho- 2: Ben, stupid, over-fired, burned, gamma-burned, benzene, toluene, xylene, etc. In the case of producing a photosensitive resin composition, the (four) baked film has excellent in-plane uniformity, and the sensitivity is high. The exposure amount and the same development time form a pattern, and the film thickness margin is wide, and the photosensitive film is exposed. The sensitizer such as a diazonaphthoquinone compound has a low precipitation property, and the stability of the composition is high, and γ-butyrolactone is preferred. ~ In the case where the organic solvent is added to the composition, the amount of addition is 1 〇〇 to 2 〇〇〇 by mass based on 100 parts by mass of the soluble resin, and the addition of the organic solvent can be changed. Amount to control viscosity. Preferably, ΐ2〇~7〇θ〇 141019.doc 201005008 Quality injury, more preferably 150~500 parts by mass. When the amount of addition is 1 part by mass or more, the viscosity of the resin composition is lowered, and the film thickness uniformity of the coating film is improved. On the other hand, when the amount of addition is 2,000 parts by mass or less, the viscosity of the resin composition is not excessively lowered. It is usually easy to apply the desired pattern film thickness. (D) Alkoxy decane compound In the resin composition of the present invention, in order to improve the adhesion to the substrate, (D) an alkoxylated compound can be added as needed. Preferable specific examples of the alkoxylation product include 3-methylpropenyloxypropyl ternary oxydecane and 3-methylpropenyloxypropyldiacoxyalkane. Base decane, 3-glycidoxypropyl tris-oxygen oxysphate, 3 _ glycidoxypropyl-oxyalkyloxycarbazide, 3-aminopropyl tri-oxylated calcined or % amine a reaction of a propyl acetoxyalkyl decane with an acid anhydride or an acid dianhydride; a 3-aminopropyl bis- succinyl sulphate or a 3-aminopropyl bis oxyalkyl sulphide The amine group is converted into a urethane group or a urea group. Examples of the thiol group in this case include a methyl group, an ethyl group, and a butyl group; examples of the acid anhydride include cis-butyl hydrazine anhydride and phthalic anhydride; and examples of the acid dianhydride include pyromellitic acid. Anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, etc.; An oxyamino group or the like; and a ureido group, a phenylaminocarbonylamino group or the like can be given. As a preferred (D) alkoxylated cerium compound, when the photosensitive resin composition is formed, the pattern is well adhered to the substrate during development, and the adhesion to the substrate after heat curing is improved. The reactivity of the sensitizer such as the photosensitive diazonaphthoquinone compound in the photosensitive resin composition is low, and the composition 141019.doc -47·201005008 has a high stability over time, preferably the following Alkoxydecane compound. 〇P Η (8) {wherein, XAX2 represents a divalent organic group, X3 and X4 represent an i-valent organic group, and s represents an integer of 0 to 2}; [Chem. 62] (Xe-Ob-- (Χ5)* Η Ο Si-Χτ-Ν—Cx ^COOH HOO〆−X»-Si—(I Ut») :0—Xu)js t〇)s (9) {wherein, X7 and X9 represent 2 a valence organic group, χ8 represents a tetravalent organic group, χ5, X6, Χίο and Xl 1 represent a monovalent organic group, and s represents an integer of 〇~2}; [Chem. 63]

NH-Xij-Si-·(〇—Xj5)3.s (ΧιΛ (1 0) {wherein, Χΐ3 represents a divalent organic group, χ12, Χ14&ΧΙ5 represents a monovalent organic group, and s represents an integer of 0 to 2 And t represents an integer of 0 to 5}; [Chem. 64] Ο Η

Xi6~C 一Ν—X”^'"Si—(OXj^-s (ΧιΑ (1 1) { where x is 6 -nh-r20 or -〇-r21 (here, r20, and R21 Is a monovalent organic group containing no COOH group, Xi7 represents a divalent organic group, 乂18 and 乂19 are shown in Table 141019.doc 48-201005008 shows a monovalent organic group, and s represents an integer of 〇~2}; ]

HS—X22—^i—(〇X24>3.S (12) (X23), and {wherein, X22 represents a divalent organic group, X23 and X24 represent a monovalent organic group and s represents an integer of 〇~2}化 H2N-C-NH-X25—Si—(〇Χ27)^0 (ΧΜ), (13) and {wherein, Χ25 represents a divalent organic group, and x26 and χ27 represent a monovalent organic group. s represents an integer of 0 to 2}; [Chem. 67] ((知购

^29*~X: 30—ΪΪ—(〇X32)3*S (X3l)s (14) ❿ {wherein, Xu represents a hydrogen atom or a fluorenyl group, and χ29 represents a valence selected from the group of the following formula: Group: [Chem. 68]

0 0 —ch2-- S〇2"~~ — -OC-NH- 11 --C-NH 0 Η 0 w --NH-C· 0 —NH-C-NH II 0--C- 0 II — -C-O-- 0 II -oc- ~c-- 0 II cf3 , X3〇 represents a divalent organic group, χ31&χ32 represents a monovalent organic group, s represents an integer of 0~2, and u represents 1~3 Integer}; 141019.doc -49- 201005008 [Chem. 69]

\一7^~X33-X34-Si~(〇X36>3-S (10) (15) {wherein, X33 is the same as X29 defined in the general formula (14), χ34 represents a divalent organic group, and X35 and Xu represent A monovalent organic group, and s represents an integer of 〇~2). The amount of the (D) alkoxydecane compound to be added is preferably in the range of 0.01 to 2 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. (E) a compound which undergoes crosslinking reaction by heat in the resin composition of the present invention, in order to increase the glass transition temperature of the film after thermosetting, or to improve solvent resistance to various organic solvents, it may be added by heat as needed A compound of a crosslinking reaction (hereinafter also referred to as a thermal crosslinking agent). Here, as the temperature at which the crosslinking reaction is caused, it is preferably 15 〇 to 35 〇 °C. The crosslinking reaction is produced by heat treatment after patterning by development. As a specific component, it is preferably selected from the group consisting of a compound having an epoxy group, a methyl group, an alkoxymethyl group, or an epoxybutyl group, and a di-bromopropyl dinadiimide compound. At least one compound. As the octaethoxy group-containing compound, specifically, a double-type A type epoxy: a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a cresol novolac type epoxy resin, a benzene secret. Varnish type epoxy resin, glycidylamine type epoxy resin, polysulfide type cyclic resin. As a compound having a methylol group or a compound having an alkoxymethyl group. It is preferably a compound having two or more monovalent organic groups represented by the formula (A) in the molecule. 141019.doc 201005008 [10] (3), (A) {wherein, E! is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms} A compound having a methylol group or having an alkoxymethyl group Among the compounds, a compound having an alkoxymethyl group is preferred from the viewpoint of viscosity stability when stored in a photosensitive resin composition at room temperature. Among the compounds having a methylol group or a compound having an alkoxymethyl group, more preferably A is selected from the group consisting of a compound having a phenolic hydroxyl group, a compound containing a divalent organic group represented by the formula (B), and At least one compound of the group consisting of the compounds represented by the formula (C). [化71] Ψ 〇 tH -

In the formula, E2 is a hydrogen atom or an alkyl group having a carbon number of 1 to 6} [Chem. 72]

In the formula, E3 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. 141019.doc -51 - 201005008 The compound having a phenolic hydroxyl group is exemplified by the following compounds. [化73]

[化74]

H3COH2C CH^OCH) 141019.doc -52- 201005008

The compound containing the divalent organic group represented by the formula (B) includes the following compounds. These may be used alone or in combination of plural. H3coh2c-nh-c-nh-ch2och3

H3CH2COH2C-NH-C-NH-CH2OCH2CHj H3COHb νΆ N___cH20CHj HjCHjO OCH2CH3 H5CHjCOIt-N^N ^〇h2〇CH2CH3

HjCOH2C, human /CH2〇CH3 N

Η3<Χ>Η2(^ 丫, ch2〇CHj o H}CH20 OCHjCHj — again, one 3

H

HjCH2COH2cf 丫, CH2〇CH;>CH3

O

The E2 of the formula (B) is a monovalent organic group, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably a carbon number of 1 to 10 in terms of solubility of the resin composition. The alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms. The compound containing a divalent organic group represented by the formula (C) includes the following compounds. [化76]

141019.doc -53- 201005008 The valence organic group of the formula (C) is preferably an alkyl group having a carbon number of 丨~2〇, and more preferably a carbon in terms of solubility of the composition of the tree The number of the base is 1 to 1 Torr, and more preferably the base having 1 to 4 carbon atoms. The compound having an epoxybutyl group is specifically a compound having one or more four-membered cyclic ether structure in a molecule, and can be subjected to cationic ring-opening polymerization, or a solubilizing acid, a mercaptan or a benzene. Addition reaction. For example, 1,4-bis{[(3_ethyl_3_epoxybutyl)methoxy]methyl) phenyl, bismuth-ethyl(3-epoxybutyl)methyl , 4,4._bis[(3_ethyl-whenepoxybutyl)methoxymethyl]biphenyl, 4,4,_bis(3_ethyl_3_epoxybutylmethoxy)biphenyl Ethylene glycol bis(3·ethyl_3_epoxybutylmethyl ice, ethylene glycol bis(3-ethyl·3-epoxybutylmethyl m, bis(3_ethyl·3 epoxybutylmethyl) ) dip vinegar, trimethyl propyl acetonate (3_ethyl _3 epoxy butyl methyl) shout, pentaerythritol tetrakis (3 · ethyl _3_epoxy butyl methyl) shout, poly [[3[( 3 ethyl _ 3 · epoxybutyl) methoxy] propyl] decyl sesquioxide] derivative &, oxalic acid oxetane vinegar, phenol novolac oxetane, ^ - double "Hyperyloxycyclobutane-3_yl)methoxy]benzene, etc., but is not limited thereto. These may be used singly or in combination of plural. The compound may, for example, be exemplified by the following compounds.

141019.doc -54- 201005008

°Hai can be used alone or in combination. In the case of containing (E) the amount of the compound which undergoes the crosslinking reaction by heat, the cross-linking effect 'is related to the pattern deformation of the post-development heat treatment and the remnant generated during development (in terms of the allowable amplitude of the float) The optimum addition amount is selected according to the selected crosslinking agent. The amount of the soluble resin is preferably 〇5 to 50 parts by mass, more preferably 5 to 30 parts by mass, relative to (4) the soluble resin. At least one compound of a group consisting of a free acrylic brewing compound, an f-based acrylic acid vinegar compound, an allyl-containing compound, a f-oxygen-containing compound, and a phenylacetic acid compound

In the resin ν σ of the present invention, it is also possible to protect the human & heart according to the kind or molecular weight of the polymer. The alkali dissolution rate of the substance can be developed within a range of an appropriate development time. The method contains the above compound (F). As the acrylic acidified human plate, the methyl acetoacetate compound may be selected from the group consisting of propylene vinegar, yin yin, acrylamide, and methacrylic acid 141019.doc -55- 201005008 A compound in a group consisting of amines. As a preferable specific example, NK-ester series M_20G, M-40G, M-90G, M-230G, CB-1, SA, S, AMP-10G, AMP-20G manufactured by Shin-Nakamura Chemical Industry Co., Ltd. , 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, A-HD, A-NPG, APG-200, APG-400, APG-700, A-BPE-4, 701A, TMPT, A-TMPT , A-TMM-3, A-TMM-3L, and A-TMMT. Moreover, the 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, 1.9ND, TMP, G-101P, G-201P, BP-2EM, TB, IS, MTG, BO, CL, 3EG, 4EG, 9EG, 14EG, NP, M-3F, M-4F , M-6F, FM-108, 1.3BG, 1.10DC. Moreover, the Light acrylate series IAA, L_A, SA, BO-A, EC-A, MTG-A, 130A, DPM-A, PO-A, P-200A, NP-4EA, which are manufactured by Kyoeisha Chemical Co., Ltd., may be mentioned. NP-8EA, THF-A, IB-XA, HOA, HOP-A, M-600A, HOA-MS, HOA-MPE, 3EG-A, 4EG-A, 9EG-A, 14EG-A, NP-A, 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, 141019.doc -56- 201005008 G-201P. Further, examples thereof include Epoxy ester series manufactured by Kyoeisha Chemical Co., Ltd. ^!-600A, 40EM, 70PA, 200PA, 80MFA, 3002M, and 3002A. Further, examples thereof include Aronix series Μ-101, M-102, M-110, M-111, M-113, M-117, M-120, M-208, M-210, M- manufactured by East Asia Synthetic Co., Ltd. 211, M-215, M-220, M-225, M-233, M-240 'M-245 ' M-260 ' M-270 ' M-305 ' M-309 > M-310, M-315 , M-320, M-350, M-360, M-400, M-408, ❹ M-450, M-5300, M-5400, M-5600, M-5700 ° DMAEA, DMAPAA, DMAA, ACMO, NIPAM, DEAA, etc. These compounds may be used singly or in combination of two or more. Examples of the compound containing a dilute propyl group include decyl alcohol, propyl benzophenone, allyl benzoate, allyl cinnamate, N-allyloxyphthalimide, and alkene. Propylphenol, allylphenyl hydrazine, allyl urea, diisopropyl phthalate, diallyl isophthalate, di-allyl terephthalate, maleic acid Diallyl ester, diallyl isocyanurate, triallylamine, triallyl isocyanurate, triallyl cyanurate, triallylamine, 1,3, Triallyl 5-benzenetrianoate, triallyl-trimellitic acid ester (TRIAM705 manufactured by Wako Pure Chemical Industries, Ltd.), triallyl pyromellitic acid (TRIAM805 manufactured by Wako Pure Chemical Industries, Ltd.) , triallyl oxydiphthalate, triallyl phosphate, triallyl phosphite, triallyl citrate. These compounds may be used singly or in combination. Examples of the methoxy group-containing compound include the following compounds. 141019.doc -57- 201005008 [化78]

The following compounds are mentioned as a phenyl ester compound. [化79]

The compounding amount of the (F) compound is preferably from 0.5 to 50 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. From the viewpoint of obtaining a sufficient effect of inhibiting the dissolution, it is preferably 5 parts by mass or more. On the other hand, from the viewpoint of ensuring the film thickness of the target cured film, it is preferably 50 parts by mass or less. 141019.doc -58- 201005008 (G) An organic compound having a carboxyl group in the molecule (hereinafter also referred to as "carboxy acid compound"). In order to increase the sensitivity, it may be added to an organic compound having a carboxyl group in the molecule. Specifically, a tickic acid compound having a carbon number of 4 to 2 Å is preferred, and a linear structure, a branched structure, or a cyclic structure is preferred, and the carbon number of the organic group is 6 to 12 . Specific examples thereof include sorbic acid, lauric acid, meat ugly acid, adipic acid, 2-mercapto-4-enoic acid, 4-methyl-2-pentenoic acid, and 2-methyl-2. -Pentenoic acid, 2-methyl-n-valeric acid, 3-methyl-n-valeric acid, _4-methyl-n-valeric acid, 2-ethylbutyric acid, heptanoic acid, octanoic acid, n-decanoic acid, iso Capric acid, citric acid, DL-leucine, 2-heptanoic acid, 2-octenoic acid, 2-indole acid, 2-decenoic acid, 9-decenoic acid, 2-dodecenoic acid, ι 〇_undecenoic acid, 3-cyclohexene-1-decanoic acid, 1-cyclohexene-3-carboxylic acid, cyclohexanoic acid, cyclopentaacetic acid, cyclohexanoic acid, cyclohexanoic acid, 4-cyclohexidine Acid, 5_norbornene_2_carboxylic acid, p-methoxybensic acid, 2,4-di-perbenzoic acid, 3,5-di-perbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, O-methoxybenzoic acid, m-methoxybenzoic acid, p-methoxy benzoic acid, salicylic acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 3-phenyl lactic acid , 4-hydroxyphenyl lactic acid, 4-hydroxymandelic acid, 3,4-dihydroxymandelic acid, 4-hydroxy-3-methoxylated mandelic acid, 2-methoxy-2-(1-naphthyl)propene Acid, mandelic acid, benzene Acid, acetyl mandelic acid, alpha] Yue methoxyphenyl acetate. Among these carboxylic acid compounds, in order to improve the sensitivity and to be high in adhesion to the substrate of the pattern at the time of development, m-benzoic acid or α-methoxyphenylacetic acid is particularly preferable. (G) The compounding amount of the organic compound having a slow-base in the molecule is preferably from 1 to 30 parts by mass based on 100 parts by mass of the (base) alkali-soluble resin, more preferably 141019.doc -59-201005008 is 5~ 10 parts by mass. When the amount of the carboxylic acid compound is at least i part by mass, the development residue of the exposed portion is reduced, the sensitivity is also improved, and the adhesion to the ruthenium substrate is also good; and the other φ is 3 Å or less by mass. The film is less reduced during hardening, and the film has a good elongation after hardening. (Other Additives) In the photosensitive resin composition of the present invention, a dye, a surfactant, a dissolution promoter, a bonding aid, or the like may be added as needed. Further, the above additives will be specifically described as the dyes, and examples of the dyes include fluorenyl violet, crystal violet, and malachite green. The amount of the dye added 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. In addition, examples of the surfactant include nonionic surfactants such as polydiamides such as polypropylene glycol and polyoxyethylene lauryl ether, and derivatives thereof, uorad (manufactured by Sumitomo 3m Co., Ltd.), Megaface (manufactured by Sumitomo 3m Co., Ltd.) A trade name, manufactured by Otsuka Ink Chemical Industry Co., Ltd., a fluorine-based surfactant such as Sulfl〇n (trade name, manufactured by Asahi Glass Co., Ltd.), KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, chisso company) Manufacturing),

An organic oxoxane interface such as Glan〇l (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) is a bioactive oxoxane surfactant. From the viewpoint of no fluorine, it is preferably an organic oxoxane surfactant. The amount of the surfactant to be added is preferably in the range of 0.01 to 5.0 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. Further, as the dissolution promoter, a compound having a phenolic hydroxyl group is preferably, for example, a straight-chain type such as dip, Mtris PC or Mtetra PC. 14I019.doc 201005008 Phenolic compound (manufactured by Bento Chemical Industry Co., Ltd.), Tris a non-linear phenol compound such as p_HAp, THs p_ ΡΗΒΑ, or Tns P-PA (manufactured by Honshu Chemical Industry Co., Ltd.), 5-n-hexyl resorcinol, and a hydrogen atom of a phenyl group of diphenylmethane is substituted with a hydroxyl group. a compound obtained by substituting 1 to 5 hydrogen atoms of a phenyl group of 3,3 diphenylpropane with a hydroxyl group, bis(3•amino-4-hydroxyphenyl)sulfone and ι,2-ring丨 of dicarboxylic anhydride: 2 reactants and the like. The amount of the addition of the dissolution promoter is preferably in the range of from 0 5 to 20 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. 0 Further, a bonding aid for improving the adhesion can be added. Examples of such a secondary auxiliary agent include alkyl imidazoline, butyric acid, polyhydroxystyrene, polyvinyl methyl ether, third butyl novolac, epoxy decane, epoxy polymer, and 3- Aminopropyltriethoxylate is burned. The addition amount in the case where the auxiliary agent is added is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the (A) alkali-soluble resin. <Detailed Description of Negative Photosensitive Resin Composition> The (A) alkali-soluble resin of the present invention contains (H) a compound which generates an acid by irradiation with a living light, and (I) an acid which can be utilized A negative photosensitive resin composition can be produced by a compound which crosslinks the resin. The details will be described below. (H) A compound capable of generating an acid by irradiation with active light (H) A compound which can generate an acid by irradiation with active light is a compound which can produce an acid by irradiation with active light, and as such a compound, for example The following compounds are listed. i) Dimethyl sulfhydryl-s-triazines 141019.doc -61- 201005008 Tris (2,4,6-trimethylmethyl) are all called, 2-phenyl-bis(4,6-trimethyl) Homotriazine, 2-(3-chlorophenyl)-bis(4,6-trimethylmethyl)-s-triazine, 2-(2-hydroxyphenyl)-bis(4,6-trimethylsulfonyl) -s-triazine, 2-(4-methoxyphenyl)_bis(46_trimethylsulfonyl V-s-triazine, 2-(3-methoxyphenyl)-bis(4,6-trisole) Base) _ s-triazine, 2-(2-decyloxyphenyl)-bis (4,6-trimethyl fluorenyl) s-triazine, 2-(4-mercaptothiophenyl)-bis (4, 6-trimethylmethyl)-s-triazine, 2-(3-methylthiophenyl)bis(4,6-trichloromethyl-s-triazine, 2-(2-methylthiophenyl)- Bis(4,6-trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-bis(4,6-trimethylmethyl)-s-triazine, 2-(3-A Oxynaphthyl)-bis(4,6-trimethylmethyl)-s-triazine, 2-(2-methoxynaphthyl)-bis(4,6-trimethylmethyl)-s-triazine, 2-(3,4,5-trimethoxy-β-styryl)-bis(4,6-trimethylmethyl)-s-triazine, 2-(4-methylsulfanyl-β-styryl) - bis(4,6-trichloromethyl)-s-triazine, 2-(3-methylsulfanyl-β-styryl)-double 4,6·trichloroindenyl)-s-triazine, 2-(2-methylsulfanyl-β-styryl)-bis(4,6-trimethylmethyl)-s-triazine, etc. ii) II Allyl quinone diphenyl sulfonium tetrafluoroborate, diphenyl sulfonium tetrafluorophosphate, diphenyl sulfonium tetrafluoro arsenate, diphenyl sulfonium trifluoromethanesulfonate, diphenyl fluorene trifluoride Acetate, diphenylphosphonium p-toluenesulfonate, 4-methoxyphenylphenylphosphonium tetrafluoroborate, 4-decyloxyphenylphenylphosphonium hexafluorophosphonate, 4-nonyloxybenzene Phenyl phenyl hexafluoroarsenate, 4-methoxyphenyl phenyl sulfonium trifluoromethanesulfonate, 4-decyloxyphenylphenyl fluorene trifluoroacetate, 4-decyloxyphenylbenzene Base oxime benzenesulfonate, bis(4-t-butylphenyl)phosphonium tetrafluoroborate, bis(4·t-butylphenyl)phosphonium hexafluoroarsenate, double (4-third Butylphenyl) fluorene triflate, bis(4-t-butylphenyl)phosphonium trifluoroacetate, bis(4-tert-butyl 141019.doc -62· 201005008 phenyl) fluorene- P-toluenesulfonate, etc. iii) triallyl salt-dissolving triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate , triphenylsulfonium sulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxy Phenyldiphenylphosphonium hexafluorophosphonate, 4-methoxyphenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium sulfonate, 4-methoxy Phenyldiphenylphosphonium trifluoroacetate, 4-decyloxyphenyldiphenylfluorene φ p-toluenesulfonate, (4-phenylthio)phenyldiphenylphosphonium tetrafluoroborate, (4- Phenylthio) phenyldiphenylphosphonium hexafluorophosphonate, (4-phenylthio)phenyldiphenylphosphonium hexafluoroarsenate, (4-phenylthio)phenyldiphenylphosphonium trifluoride Methanesulfonate, (4-phenylthio)phenyldiphenylphosphonium trifluoroacetate, (4-phenylthio)phenyldiphenylphosphonium p-toluenesulfonate, and the like. Among these compounds, examples of the tris-mercapto-s-triazines include 2-(3-chlorophenyl)-bis(4,6-trichloroindenyl)-homo-trimium, 2-(4- Chlorophenyl)-bis(4,6-trimethylmethyl)-s-triazine, 2-(4-mercaptothiophenyl)-bis(4,6-trimethylmethyl)-s-triazine, 2-(4-decyloxy-β-styryl)-bis(4,6-trichloromethyl)-s-triazine, 2-(4-decyloxynaphthyl)-bis(4,6- Trichloroindolyl)-s-triazine or the like is preferred; as the diarylsulfonium salt, diphenylsulfonium trifluoroacetate, diphenylsulfonium trifluoromethanesulfonate, 4-methoxy Phenylphenyl fluorene trifluoromethanesulfonate, 4-methoxyphenyl phenyl fluorene trifluoroacetate, and the like are preferred examples; and as the triarylsulfonium salt, triphenylsulfonium sulfonic acid is exemplified. Salt, triphenylsulfate trifluoroacetate, 4-decyloxyphenyldiphenylphosphonium sulfonate, 4-decyloxyphenyldiphenylphosphonium trifluoroacetate, (4-phenylsulfide) Phenyldiphenyl 141019.doc -63-201005008 A sulfonium triflate sulfonate, (4-phenylthio)phenyldiphenylphosphonium trifluoroacetate or the like is preferred. Further, the compounds shown below can also be used. (1) The diazoketone compound, as the diazoketone compound, for example, a ruthenium diquinone diazonium compound, a diazonium quinone compound, a diazonaphthoquinone compound, etc., and specific examples thereof may be mentioned. 2. Cai brewed two stacks of gas _4_ rubic acid vinegar compound. (2) The ruthenium compound as the hindrance compound is exemplified by a β_steel wind compound, a β·continuation barrier compound, or an α_heavy gas compound of such a compound. As a specific example, it can be cited as: 4_triphenyl Methyl, benzoyl benzoate, bis (phenyl sulfonyl) methane, etc. (3) a sulfonic acid compound as a reductive acid compound, for example, can be described as a sulphuric acid alkyl ester, a sulfonic acid haloalkyl ester, a sucrose aryl ester, K Im imidosulfonates and the like. As a preferred specific example, there may be mentioned: An Ziweitian # I^ N. sinensis sulfonate, pyrogallol trifluoroformate, o-nitroguanidine trifluoromethanesulfonate曰, p-nitrobenzyl benzyl p-toluenesulfonate (4) sulfonimide compound as a specific example of the ruthenium imine compound, for example, N_(three said methyl decyloxy) butyl sulfoxide , N_(trifluoromethyl ethoxylated) phthalimide, Nd methyl ethoxy) dipyridinium diimide diamine, N_(trifluoromethyl hydroxy) oxy ring [eg, such as - di- 仏 叛 叛 酿 酿 亚, called trifluoromethylsulfonyloxy) naphthyl quinone imine and so on. 141019.doc -64 · 201005008 (5) The oxime ester compound can be exemplified by 2-[2-(4.methylphenylsulfonyloxyimino)]_2,3_dihydrothiophene-3-ylidene] -2-(2-mercaptophenyl)acetonitrile (trade name "Irgacure PAG121" by Ciba Specialty Chemicals Co., Ltd.), [2-(propyl hydroxyanilide)-2,3- Dihydroseptin-3-ylidene]-2-(2-methylphenyl)acetonitrile ('/Feiba Refinery Company's trade name "Irgacure PAG 1 〇3") and the like. (6) Diazomethane compound Specific examples of the diazonium compound include bis(trifluoromethylsulfonyl)diazononane, bis(cyclohexylsulfonyl)diazomethane, and bis. (phenylsulfonyl) diazonium and the like. Particularly, from the viewpoint of sensitivity, the above (5) oxime ester compound is preferred. (H) The amount of the compound which can generate an acid by irradiation with active light is preferably from 0.5 to 30 parts by mass, more preferably from 0.5 to 30 parts by mass, based on 1 part by mass of the heat-resistant polymer containing the copolymer of the present invention. Buchuan quality. When the amount of addition is 5% by mass or more, the amount of acid which can be generated by irradiation of the active light is sufficiently increased, and the sensitivity is improved. On the other hand, if the amount is 3 parts by mass or less, the hardening is performed. The mechanical properties will not decrease afterwards. (I) A compound which can crosslink the resin by the action of an acid. Hereinafter, the compound (I) which can crosslink the above heat-resistant polymer by the action of an acid will be described. When a compound which can crosslink the polymer by the action of the acid is added, when the coating film is heat-hardened, the (A) heat-resistant polymer can be crosslinked or form a crosslinked network by itself, thereby enhancing heat resistance. . (I) The compound component which can crosslink the polymer by the action of an acid is preferably 141019.doc -65- 201005008 is a melamine resin selected from the group consisting of a hydroxymethyl group or an alkoxy fluorenyl group at the N position and a monomer thereof And urea resin and its monomers. Examples of such an alkoxylated melamine resin, an alkoxymethylated benzene melamine resin, an alkoxylated guanidine urea resin, an alkoxymethylated gland resin, and the like Wait for the monomer. Among these, alkoxymethylated melamine resin, alkoxylated phenyl melamine resin, alkoxymethylated glycoluril resin, alkoxy-based urea resin, and the like It is obtained by converting a correspondingly known methylated melamine resin, methylated benzoguanamine resin, hydroxymethylated urea resin, and a methylol group thereof into an alkoxymethyl group. Examples of the type of the alkoxymethyl group include a methoxy fluorenyl group, an ethoxylated fluorenyl group, a propoxymethyl group, a butoxymethyl group, and the like, which can be preferably used commercially. Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156 1158, 1123, 1170, 1174, UFR65, _ (Mitsui Cytec), Nikalac MX -270, -280, -290, Nikalac MS-11,

NikaUc MW-30, _100, _3〇〇, _39〇, _75〇 (made by Sanwa Chemical Co., Ltd.). These compounds may be used singly or in combination. The monomer of the above-mentioned resin can also be used as a crosslinking agent, and examples thereof include hexamethoxymethyl tripolyamine, dimethoxymethyl gland and the like. The amount of the compound (1) which can be crosslinked by the action of an acid is preferably 1 part by mass or less, more preferably 5 to 30 parts by mass based on 1 part by mass of the (A) alkali-soluble resin. When the amount of addition is 3 parts by mass or more, the crosslinking can be sufficiently carried out on the one hand, and if the added patterning property is good; and the amount of 141019.doc -66 · 201005008 is 50 parts by mass or less, the mechanical after curing can be maintained. Physical properties. Further, in the negative photosensitive resin composition, (6) an organic solvent, (D) a secondary auxiliary agent, and (8) a crosslinking reaction with the resin of the present invention by heat may be added as needed. Compound, (other additives). <Method of Forming Hardened Convex Pattern> The following discloses a method of forming a hardened relief pattern on a substrate by using the photosensitive resin composition of the present invention (hereinafter, also referred to as "this" An example of the method"). ^, First, a coating step of forming the composition on a substrate in the form of a layer or a film. The substrate is applied, for example, to a Shihwa wafer, a ceramic substrate, an aluminum plate, or the like. In this case, in order to improve the adhesion between the formed relief pattern and the substrate, a bonding aid such as a squeezing coupler may be applied to the substrate in advance. The coating method of the composition is applied by spin coating using a spinner. The cloth is sprayed, sprayed, printed, rolled, or the like using a sprayer. Next, the following exposure steps are carried out: after the pre-bake is performed for 8 to 14 generations, the coating film is dried, and the contact alignment machine, the mirror projection exposure machine, the stepping unicorn exposure device are used, and the chemical line is used through the mask. The layer or film is exposed or directly irradiated with light, electron beams or ion lines. As the chemical line, X-rays, electron beams, ultraviolet rays, visible rays, or the like can be used, and those having a wavelength of 200 to 500 nm are preferred. In terms of resolution and operability of the pattern, the wavelength of the light source preferably includes an i-line, and more preferably is an i-line alone. As the exposure device, a contact aligner, a mirror caster, a stepper, and a stepper are particularly preferable. Next, in the case of the negative photosensitive composition only, after exposure, it is heated again at 141019.doc •67·201005008 8〇~140°C for 3 seconds to 6 seconds. This is called post-exposure bake (also referred to as PEB, post exp〇sure bake). D is used to cause the acid generated by the exposure to become a catalyst, and the exposed portion (1) can utilize the action of an acid to make the heat resistance described above. The polymer crosslinked compound causes a thermal crosslinking reaction to become insoluble in an aqueous alkali solution. Next, in the case of a positive photosensitive composition, a developing step of eluting and removing the exposed portion by a developing solution is performed. In the case of a photosensitive composition, a development step of eluting and removing the unexposed portion by a developing solution is performed. The developing method can be selected from methods such as a dipping method, a stirring method, and a rotary spray method. As the developer, an inorganic base such as sodium hydroxide, sodium carbonate, sodium citrate or ammonia water, an organic amine such as ethylamine, diethylamine, triethylamine or triethanolamine, tetramethylammonium hydroxide or the like can be used. An aqueous solution of a quaternary ammonium salt such as tetrabutylammonium hydroxide or the like, and if necessary, a water-soluble organic solvent such as methylcellulose or ethanol or an aqueous solution containing an appropriate amount of a surfactant may be used. Among them, a preferred aqueous solution of tetramethylammonium hydroxide has a concentration of 〇·5% to 10%, more preferably i 〇% to 5%, particularly preferably 238%. This concentration is used in the semiconductor fabrication steps. After development, the eluent can be used for cleaning. The developer is removed, whereby a relief pattern formed on the substrate is obtained. As the eluent, distilled water, methanol, ethanol, isopropyl alcohol or the like may be used singly or in combination. Finally, a heating step of heating the relief pattern of the alkali-soluble resin thus obtained is carried out. The heating temperature is preferably 18 or more (rc or more. Usually, it is heated to 250. (: ~400t: 'The component which has low heat resistance contained in the additive component is decomposed, vaporized, and converted by dehydration and cyclization reaction. For the stupid and 141019.doc -68 - 201005008 chews 'this change is the sturdy resistance,,,, I Wang 衩 embossed pattern. As such a heat treatment device, a heating plate, a supply box, It can be used for the temperature-increasing drying of the temperature program. _ ', the air can be used as the ring body for heat treatment, or the inert gas such as nitrogen rolling or argon gas can be used for gas rolling. When the heat treatment is performed under a low degree of water, the vacuum pump can be used to equalize the addition under reduced pressure. The resin of the present invention can be used at a lower temperature of 250 ° C than the previous PB ◦ precursor resin. + Anti-division of the pair and the dehydration ring-closing reaction of oxazole, the mechanical elongation is also close, wind /

Handcuffs will exceed 40%. This situation is also better in improving the reliability of the semiconductor device. A semiconductor device can be manufactured by combining the above-described method of forming a cured relief pattern with a semiconductor device manufacturing method which is well known as a buffer film for a semiconductor device or a method for forming an interlayer insulating film. [Embodiment] Hereinafter, an example of an embodiment of the present invention will be described in detail with reference to four columns, examples, and comparisons. &lt;Reference Example 1 &gt; (Manufacture of bis(gas carbonyl)tricyclo[5,2,1,〇2'6] simmered) Glass to which a stirrer of the iron type (registered trademark) is attached In a separable three-necked flask, 7 9 g (〇366 mol) of tricyclo[5,2,1,02'6]decane dimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in il acetonitrile. a solution obtained by dissolving 256.7 g (l.808 mol) of disodium hydrogen phosphate and 217_1 g (1.809 mol) of sodium bisulphate in ion-exchanged water of 丨4 l as a reaction Solution. Add 2.8 (0.0179 mol) of 2,2,6,6-tetramethyl 唆-1_ oxygen (manufactured by Tokyo Chemical Industry Co., Ltd. 141019.doc •69·201005008, the following, also 艋* π The nickname "TEMPO")' is stirred to dissolve. With 850 ml of miscellaneous & 〈 < ion father water will be 143.2 g (l.267 mol) of 80. / 〇 subgas is diluted with sodium sulphate and added dropwise to the above reaction solution. Then, a cold droplet of 3 ml of a 5 % aqueous solution of sodium sulphate was diluted with 7 ml of ion-exchanged water to the reaction liquid. The reaction solution was maintained at 35 to 38 C by a constant temperature layer and stirred for 2 hours to cause a reaction. After the reaction, the reaction solution was cooled to 12 ° C, and an aqueous solution of 75 g of sodium sulfite cooled in 300 ml of ion-exchanged water was added dropwise to the reaction solution, and after the excess sodium sulfite was deactivated, 5 〇 was obtained. The ethyl acetate in liters was rinsed. Thereafter, 115 ml of 1% by weight hydrochloric acid was added dropwise, and the pH of the reaction liquid was adjusted to 3 to 4, and the precipitate was recovered by decantation. The precipitate was dissolved in 2 mL of tetrahydrofuran. Further, the aqueous layer was extracted with 5 ml of acetic acid, and then washed with brine, and the precipitate was dissolved in a solution of tetrahydrofuran in the same manner. The above tetrahydrofuran solution was mixed and dried over anhydrous sodium sulfate. The solution was concentrated and dried using an evaporator to obtain 5 8.4 g (yield: 71 1%) of bis(carboxy)tricyclo[5 21 〇 2, white crystals of decane. 62.5 g (278 mmol) of bis(carboxy)tricyclo[5,2,1,〇2'6]decane, 97 ml (1.33 mol) of sulfite, ruthenium obtained in this way. 4 ml (5. 〇 mmol) is put into the reaction vessel and mixed at 25~50 〇C for 18 hours to react. After the reaction is completed, add toluene 'under reduced pressure' to make excess The sulfite gas was azeotroped with toluene, thereby being concentrated to obtain 73.3 g (yield 100%) of an oily bis(cyclocarbonyl)tricyclo[5,2,1〇2,6] anthracene. 141019.doc •70-201005008 &lt;Reference Example 2&gt; 271 g (i5 mmol) of 5-aminoisophthalic acid (manufactured by Merck) was dissolved in a 100 ml two-necked flask made of glass. a solution of 3 〇g of N_methyl-2-pyrrolidone and 2.37 g (30 mmol) of pyridine, to which 1.79 g (15.7 mmol) was dissolved in 54 § Ethyl formate in 7-butyrolactone (manufactured by Tokyo Chemical Industry Co., Ltd.). Cool the ice bath to 0 ° C so that the temperature does not exceed 1 (TC), add 5 35 g (3 drops) in 3 minutes. Sulphur dissolved in 15 § 7-butyrolactone The gas was cooled in an ice bath at a temperature of more than 10 ° C, and after stirring for 1 hour, it was returned to room temperature, and the unreacted sulfite chlorine and the by-product sulfurous acid gas were distilled off using a vacuum pump. The γ-aminoisophthalic acid derivative was synthesized. This was used as the reaction liquid 1. <Reference Example 3> To a separable three-necked flask made of glass, 19 42 g (1 Torr of millimolar) was added. 3-benzene diacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 77 g of N-methyl-2-pyrrolidinone (hereinafter also referred to as r NMP (N-methyl-2-❹)), 2 drops of N, N-dimethylformamide was dissolved by stirring with a stirrer made of Teflon (registered trademark) and a magnetic stirrer. The reaction liquid was cooled to _7 using a methanol bath cooled with dry ice. ~_ 15C ' After dropping 28.56 g (240 mmol) of sulfite (manufactured by Tokyo Chemical Industry Co., Ltd.) into the reaction solution, the reaction vessel was immersed in an ice bath and stirred for 1 hour. , using a vacuum pump, steaming unreacted sulfite chlorine and by-product sulfurous acid gas in 3 minutes. The 1,3-benzenediacetic acid derivative was synthesized by distillation, and it was used as a reaction liquid 2. 141019.doc -71· 201005008 &lt;Reference Example 4&gt; 19.80 g (115 mmol) was added to a three-necked glass flask. 1,4-cyclohexyl decanoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 6 〇g of 丫-butyrolactone, 0.28 g (1.24 mmol) of benzyltriethylamine (Tokyo Chemicals Co., Ltd.) Industrial Co., Ltd.), using a stirrer made of Teflon (registered trademark) and a magnetic stirrer' to stir and dissolve. The reaction vessel was immersed in an ice bath and cooled to 3 to 5. (:, after adding 32.84 g (276 mmol) of sulfite gas to the reaction liquid, stirring was further carried out for 30 minutes. Further, unreacted sulfoxide gas and by-products were used for 30 minutes using a vacuum pump' The sulfite gas was distilled off under reduced pressure to synthesize a 1,4·cyclohexanedicarboxylic acid derivative, and this was used as a reaction liquid 3. (Production of alkali-soluble resin) &lt;Example 1&gt; Teflon was installed (registered trademark) 1 ci 碇 ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci ci Manufactured (hereinafter, also referred to as "6FAP"), 183 g of DMAc, 55 丫 of butyrolactone, and 25 g of pyridine to dissolve it. After 6FAp is dissolved, the reaction vessel is immersed in sterol. Cooling in a container with dry ice. bis(gas carbonyl)tricyclo[5,2,1,〇2,6]decane produced in the reference example of 62. g (238 mmol) (hereinafter, Also known as "〇(:1)1)_2[〇匸1") is dissolved in 186 g of butyrolactone, kept in Hongyi, and added to the counter in (10) minutes. Should be in the container. After the dropwise addition was completed, the reaction vessel was immersed in an ice bath and kept at 0 to 1 and stirred for 3 minutes. Further, 12 5 g of pyridine was added. 141019.doc 201005008 The reaction solution was returned to room temperature, and 12.312 g of 5-norbornene anhydride was added to a π ratio of 5 · 9 3 g, and immersed in a hot water bath at 50 ° C. The reaction solution reached 50 ° C and was stirred for 18 hours. To the above reaction liquid, 310 g of ethanol and 900 g of water were added to precipitate a polymer, which was recovered and dissolved in 470 g of γ-butyrolactone. Then, ion exchange was carried out using 77 g of a cation exchange resin (Amberlyst A21, manufactured by Organo Co., Ltd.) and 95 g of an anion exchange resin (manufactured by Organo, Amberlyst 15). The solution was added dropwise to 5 liters of ion-exchanged water under high-speed mixing, and the polymer was dispersed and precipitated, and recovered, washed with water, dehydrated, and then vacuum dried to obtain a base containing a PBO precursor unit. A powder of soluble resin. One part of the solution was diluted in N-methylpyrrolidone, and a high performance liquid chromatography (hereinafter also referred to as "GPC (gel permeation chromatograph)") (Shodex KD-806M manufactured by Showa Denko, KD-806M, a tandem developing solvent N-decylpyrrolidone 40 ° C) was used to determine the molecular weight and molecular weight distribution. The analysis conditions of GPC are described as follows: ® Column: Showa Denko's trademark name Shodex 805M/ 806M series

Dissolution: N-decylpyrrolidone 40 ° C Flow rate: 1.0 ml / min Detector: 曰 分 分 制造 制造 制造 RI RI RI RI-930 The molecular weight in polystyrene conversion weight average molecular weight (Mw) is 29,300 single Sharp curve, a single composition. To the alkali-soluble resin, γ-butyrolactone was added to prepare an alkali-soluble 141019.doc -73-201005008 resin solution (P-1) having a resin concentration of 35% by mass. <Example 2> Using 58.75 g (225 mmol) of DCPD-2COC1 instead of 62.02 g (238 mmol) of DCPD-2COC1 of Example 1, the same operation as in Example 1 was carried out to obtain polystyrene. The converted molecular weight is a PBO precursor having a weight average molecular weight (Mw) of 19,000. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-2) having a resin concentration of 35% by mass. <Example 3 &gt; Using 57.12 g (219 mmol) of DCPD-2COC1 instead of 62.02 g (238 mmol) of DCPD-2COC1 of Example 1, the same operation as in Example 1 was carried out to obtain polyphenylene. The molecular weight in terms of ethylene is a PBO precursor having a weight average molecular weight (Mw) of 10,000. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-3) having a resin concentration of 35% by mass. &lt;Example 4&gt; Substituting 45.78 g (125 mmol) of 6FAP for 91.56 g (250 mmol) of 6FAP of Example 1, and using 32.3 0 g (125 mmol) of bis (3-amino group) 4--4-phenylphenyl)propanol (manufactured by Clariant Japan Co., Ltd.) (hereinafter, also referred to as "B AP"), the same operation as in Example 1 was carried out to obtain a molecular weight in terms of polystyrene. A PBO precursor having an average molecular weight (Mw) of 30,000. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-4) having a resin concentration of 35% by mass. <Example 5> 141019.doc -74- 201005008 Instead of 91.56 g (250 mmol) of 6FAP of Example 1, and a double of 16.15 g (62.5 mmol), 6FAP of 68.67 g (187.5 mmol) was used. (3-Amino-4-phenylphenyl)propane (manufactured by Clariant Japan Co., Ltd.), the same operation as in Example 1 was carried out to obtain a PBO having a molecular weight of polystyrene of a weight average molecular weight (Mw) of 29,000. Precursor. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-5) having a resin concentration of 35% by mass. &lt;Example 6&gt; φ Using 31.08 g (119 mmol) of DCPD-2COC1 instead of 62.02 g (238 mmol) of DCPD-2COC1 of Example 1, and using 35·12 g (119 mmol) 4,4'-oxybisbenzoquinone chloride (hereinafter referred to as "DEDC"), and the same operation as in Example 1 was carried out to obtain a weight average molecular weight in terms of polystyrene. PBO precursor with a molecular weight (Mw) of 33,000. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-6) having a resin concentration of 35% by mass. <Example 7> Θ DCPD-2COC1 of Example 1 was replaced with 46.61 g (178.5 mmol) of DCPD-2COC1, and 4:56 g (59.5 mmol) of the DCPD-2COC1 of Example 1 was used. 4·-oxybisbenzhydryl chloride (manufactured by Nippon Pesticide Co., Ltd.) was subjected to the same operation as in Example 1 to obtain a PBO precursor having a molecular weight of polystyrene of 31,000 and a weight average molecular weight (Mw) of 31,000. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (Ρ-7) having a resin concentration of 35% by mass. <Example 8> 141019.doc -75-201005008 To a 1 L separable three-necked flask made of glass equipped with a Teflon (registered trademark) stirrer, 54.94 g (150 mmol) was added. 6FAP, 183 g of DMAc, 550 g of γ·butyrolactone, and 25 g of pyridine were dissolved. After the 6FAP was dissolved, the reaction vessel was immersed in a sterol in which a dry ice was added to perform cooling. Next, 29.51 g (1 Torr) of dedc was dissolved in 120 g of γ-butyrolactone, kept at 5 to 2 〇t:, and added dropwise to the reaction vessel over 3 Torr. Next, 25.8 g (l〇〇 mmol) of BAp was added to the reaction bar, and after it was dissolved, 35.91 g (i38 mmol) of DCPD-2COC1 was dissolved in 108 g of γ_丁The solution in the ester was kept at 5 to -20 ° C, and it was added dropwise to the reaction vessel over 40 minutes. After the addition is complete, the reaction trough is placed in the ice, kept at 〇~1 〇 and stirred for 3 〇 minutes. Further, 12.50 g of pyridine was added. Thereafter, the same operation as in Example 进行 was carried out to obtain a PBO precursor having a molecular weight of polystyrene of 36,000 and a weight average molecular weight (Mw) of 36,000. To the alkali-soluble resin, 丫_butyrolactone was added to obtain an alkali-soluble resin solution (P_8) having a resin concentration of 35 〇/❶. &lt;Example 9&gt; A cooling tube equipped with a Dean_Stark water removing device was attached to a glass separable three-necked flask equipped with a stirrer of a Teflon (registered trademark). 18.61 g (60 mmol) of bis(34-dicarboxyphenyl)ether dianhydride (manufactured by Manac), Μ.% g〇2〇 mmol was added to 6FAp. Further, as a solvent, 110 g of γ-butyrolactone and 22 g of toluene were added. The mixture was warmed to 40 C and stirred at 1 rpm for 9 Torr under a nitrogen atmosphere. Thereafter, 150 g of ruthenium and 2.37 g (3 Torr) of pyridine were added to the reaction solution 141019.doc -76 - 201005008, and immersed in a vessel in which dry ice was added to methanol for cooling. 13.05 g (50 mmol) of DCDP-2COC1 was dissolved in 26 g of γ-butyrolactone at -5 to -10 ° C, and all was added dropwise 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, 5.53 § (70 mmol) of pyridine was added. Next, 3.28 g (20 mmol) of 5-norbornene-2,3-anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 50 ° C for 20 hours. Thereafter, heating was started in an oil bath of 180 ° C, and all the liquid was stirred at 180 rpm. During the reaction, water of φ as a by-product was azeotropically distilled off with toluene, and water accumulated in the bottom of the reflux pipe was removed every 30 minutes. After heating for 2 hours, the mixture was returned to room temperature, and a poor solvent was added to the above reaction solution to precipitate a polymer, which was then recovered and dissolved in 300 ml of NMP. Then, ion exchange was carried out with 50 g of a cation exchange resin and 50 g of an anion exchange resin. The solution was added dropwise to 2 liters of ion-exchanged water under high-speed stirring, and the polymer was dispersed and precipitated, recovered, and washed with water, dehydrated, and then vacuum dried to obtain a powder of a copolymer of PBO precursor and PI. body. A copolymer of PBO precursor and PI having a weight average molecular weight (Mw) of 21,000 in terms of polystyrene was obtained. To the alkali-soluble resin, γ-butyrolactone was added to prepare an alkali-soluble resin solution (Ρ-9) having a resin concentration of 35% by mass. <Example 10> Using DCPD-2COC1 of 54.32 g (208 mmol) instead of 62.02 g (238 mmol) of DCPD-2COC1 of Example 1, and using the total amount of the reaction liquid 1 manufactured in Reference Example 2 The same operation as in Example 1 was carried out to obtain a 141019.doc-77-201005008 PB 〇 precursor having a molecular weight of polystyrene of 28,000 in terms of weight average molecular weight (Mw) of 28,000. Γ-butyrolactone was added to the alkali-soluble resin to obtain an alkali-soluble resin solution (ρ_丨〇) having a resin concentration of 35 % by mass. &lt;Comparative Example 1&gt; As a reaction container, a separable three-necked flask made of glass to which a stirrer of Teflon (registered trademark) was attached was used. 41.75 g (U4 mmol) of 6FAP, 118 g of NMP, and 5.27 g (67 mmol) of pyridinium were added to the reaction vessel to dissolve. After the 6FAP was dissolved, the reaction vessel was immersed in methanol and added to a vessel with dry ice for cooling. The entire amount of the reaction liquid 2 produced in Reference Example 3 (1 Torr of millimolar, 3 - stupi diacetic acid derivative) was maintained at -19 to -23 ° C and all was added dropwise to the above reaction liquid. . After the completion of the dropwise addition, the reaction vessel was immersed in an ice bath, kept at 〇~丨〇, and mixed for 2 hours. Further, 10.6 g (134 mmol) of pyridine was added. Ethyl acetate was added to the above reaction solution to precipitate the polymer, which was recovered and dissolved in 3 ml of NMP. Then, ion exchange was carried out with 50 g of a cation exchange resin and 5 g of an anion exchange resin. This solution was added dropwise to 2 liters of ion-exchanged water under high-speed stirring. The polymer was dispersed and precipitated, recovered, appropriately washed with water, and dehydrated, and then vacuum-dried to obtain a powder of a PBO precursor. A PBO precursor having a molecular weight of polystyrene of 21,000 and a weight average molecular weight (Mw) of 21,000 was obtained. The test soluble resin was dissolved in N-methyl π-pyrrolidone to obtain an alkali-soluble resin solution (Ρ-11) having a resin concentration of 35 % by mass. &lt;Comparative Example 2&gt; Using 44.7 g (122 mmol) of 6FAP instead of 41.75 g (114 mmol) 6FAP of Comparative Example 1 'All of the reaction liquid 3 prepared using Reference Example 4_ 141019.doc • 78 - 201005008 Amount (115 mmol of 1,4-cyclohexanedicarboxylic acid derivative) was substituted for the reaction liquid 2, and the same operation as in Comparative Example 1 was carried out to obtain a molecular weight in terms of polystyrene as a weight average molecular weight (Mw). ) 20,500 PBO precursor. Then, the alkali-soluble resin was dissolved in N-methylpyrrolidone to obtain an alkali-soluble resin solution (p-12) having a resin concentration of 35% by mass. &lt;Comparative Example 3&gt; The same operation as in Comparative Example 2 was carried out by using 31.56 g (122 mmol) of BAP instead of 44.7 g (122 mmol) of 6FAP of Comparative Example 2, and obtained in terms of polyphenylene hydride. The molecular weight is a PBO precursor having a weight average molecular weight (Mw) of 19,500. Although γ-butyrolactone was added to the test soluble resin, gelation occurred after leaving for one night. Then, an alkali-soluble resin solution (Ρ-13) having a resin concentration of 35 mass% was obtained by dissolving the alkali-soluble resin in Ν-methyl &quot;bipiridone&gt;&lt;Comparative Example 4&gt; Add 78.48 g (280 mmol) of bis(3-amino-® 4 hydroxyphenyl)* wind to a glass separable three-necked flask of a 搅拌 type agitator (registered trademark) (Small West Chemical Industry) Manufactured by the company (hereinafter also referred to as "S02-H0AB"), and added 3 〇〇g of ν, Ν-dimethylacetamide, 14.7 g (187 mmol) of pyridine, and s〇2_h 〇AB dissolved. The reaction solution was cooled to -5 °C. Dissolve 73.45 g (249 mmol) of 4,4,-oxybi-p-methyl oxime (manufactured by Sakamoto Pesticides Co., Ltd.) (hereinafter, also referred to as "DEDC") in 2 g of γ-butyrolactone Medium, and filled into the dropping funnel', it was added dropwise to the reaction liquid in 5 minutes. After 30 minutes from the completion of the dropwise addition, 29 4 g (374 mmol) of pyridine was added. Stir at room temperature for 2 hours. Add 1〇21 g (62 mmol) of 5_降141019.doc •79· 201005008 Borneene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd. manufactures a wide side through nitrogen, - surface in a crushing bath The mixture was heated and stirred at a temperature of 5 cc under (10) for 8 hours. Thereafter, a treatment was carried out by flowing a glass column packed with 100 g of each of a cation exchange resin and an anion exchange resin substituted with 500 g of NMP. The liquid was added dropwise to 3 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water, dehydrated, and then vacuum dried to obtain a powder of an alkali-soluble resin. A single sharp curve of a weight average molecular weight (Mw) of 14500, which is a single composition. Although γ-butyrolactone is added to the test soluble resin, gelation occurs after leaving for one night. Then, the alkali-soluble resin is dissolved. In the Ν-methylpyrrolidone, an alkali-soluble resin solution (ρ_丨4) having a resin concentration of 35 % by mass was obtained. &lt;Comparative Example 5&gt; As a reaction container, Teflon was installed (registered) trademark) A separable three-necked flask made of glass of a stirrer type. 4175 g (114 mmol) of 6FAP, 118 g of NMP, and 5.27 g (67 mmol) of pyridine were added to the reaction vessel. Dissolved. After the 6FAP was dissolved, the reaction vessel was immersed in a container of dry ice and added to a sterol for cooling. 3 〇 4 g (1 〇 3 mmol) of DEDC was dissolved in 120 g of γ-butyrolactone. , kept at _i9~ -23 C ' and added to the above reaction solution. After the addition was completed, the reaction vessel was immersed in an ice bath, kept at 〇~1 (TC and stirred for 2 hours. Further added 10.6 g (134 mmol) of pyridine. Add 10.83 g of 5-norbornene anhydride to warm in a hot water bath at 50 ° C for 18 hours. Add ethanol and water to the above reaction solution to precipitate the polymer. It was recovered and dissolved in NMP of 3〇〇141019.doc •80-201005008 ml. Then, ion exchange was carried out with 50 g of cation exchange resin and 5 g of anion exchange resin. The solution was added dropwise under high speed stirring. In 2 liters of ion-exchanged water, the polymer is dispersed and precipitated, and recovered, and appropriately After washing and dehydration, vacuum drying was carried out to obtain a powder of 1 &gt; 8 Å precursor, and a PBO precursor having a molecular weight of 13,000 in terms of weight average molecular weight (Mw) in terms of polystyrene was obtained. The alkali-soluble resin was dissolved in Kenting In the inner S曰, the obtained resin concentration is 35 mass%. The soluble resin solution (P-15) is tested. φ &lt;Reference Example 5&gt; 1 L with a blender 'dropper funnel and thermometer attached In a separate flask, 30 g (〇.〇71 mol) of (2-(4-phenylphenyl)-2-propyl)phenyl)ethylidene)bisphenol was added as a polyhydroxy compound (state) A compound of the trade name Tris-PA manufactured by Chemical Industry Co., Ltd., and 1,2_naphthoquinonediazide_4_sulfonate gas equivalent to 83.3 mol% of its 〇H group 47 49 § (〇177 The solution obtained by dissolving in 3 gram of acetone was stirred and dissolved, and the flask was adjusted to 30 ° C in a strange temperature bath. Next, 17.9 g of diethylamine was dissolved in 18 g of acetone, added to the dropping funnel, and added dropwise to the flask over 30 minutes. After the addition was completed, stirring was continued for another 30 minutes, followed by dropping. Hydrochloric acid was added and the mixture was stirred for 30 minutes to complete the reaction. Thereafter, filtration was carried out to remove the triethyl hydrochloride. The ferment obtained here was added dropwise to a 3 L beaker in which 1640 g of pure water and 3 g of hydrochloric acid were stirred and stirred to obtain a precipitate. The precipitate was washed with water and filtered, and then dried at 4 (TC, under reduced pressure for 48 hours to obtain a sensitizer (ρΑ^. &lt; Reference Example 141019.doc -81 - 201005008) A glass-separable separable three-necked flask equipped with a Teflon (registered trademark) break-through stirrer was used. To the reaction vessel, 131.0 g of diacetic acid di-butane vinegar and 780 g: γ-butane s were added.曰 ' At room temperature, slowly add a solution of m8 lysine propyl oxy oxime and 270 β γ τ vinegar at room temperature. With the addition of 'reaction liquid heat up to about Fu With the progress of the reaction, carbon dioxide gas was forcibly produced. 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 (10), and the raw material was not detected at all. The purity was 98% as a single-wave peak. Thus, the auxiliary solution (di) was obtained. &lt;Reference Example 7&gt; To a three-necked flask equipped with a stirrer, a dropping funnel and a thermometer, 14.813 g was added. ((M Moer) phthalic anhydride, l47 8 g as / media GBL (y· g) and carry out #mix, adjust the flask to 30 in the strange temperature bath. Add 22.14 § (0.1 mol) of 7-aminopropyl triethoxy decane to the drip After the funnel was added dropwise to the flask over 30 minutes, and the mixture was stirred at room temperature for 12 hours to obtain the next auxiliary (D-2). &lt;Reference Example 8&gt; 5 with a blender, a dropping funnel, and a thermometer In a 〇〇m丨 three-necked flask, 16.11 g (〇.〇5 mol) of 3,3,4,4,_benzophenone tetradecanoic acid dianhydride and 153 g of GBL as a solvent were added (y_ Butyrolactone) was stirred and the flask was adjusted to 3 Torr in a thermostat. After adding 22.14 g (0.1 mol) of γ-aminopropyltriethoxylate into the dropping funnel, Add to the boiling point in 3 minutes and stir at room temperature for 12 hours to obtain the next auxiliary (D_3). 141019.doc •82· 201005008 <Reference Example 9> Attached to the mixer, dropping funnel and thermometer 5〇〇...In a three-necked flask, add 22.14 g (0.1 mol) of γ-aminopropyltriethoxyphosphonium, 116.6 g of GBL (Y_butyrolactone) as a solvent, and stir the flask. It was adjusted to 30 ° C in a temperature bath. After adding 11.9 g (0.1 mol) of isocyanic acid vinegar to the dropping funnel, it was added dropwise to the flask over 30 minutes, and the liquid temperature was raised to 50 °C. After stirring at room temperature for 12 hours, a binder (D_4) was obtained. (Preparation of photosensitive resin composition) Jane <Examples 11 to 22, Comparative Examples 6 to 10> In the combination of the following Table 1, In the alkali-soluble resin solutions (P-1 to P_15) obtained in Examples 1 to 1 and Comparative Examples 1 to 5, the amount of the pure component of the soluble resin resin was 1 part by mass, as described in Table 1. After adding the photosensitive diazonaphthoquinone compound PAC_1 obtained in Reference Example 5, and dissolving it, 4 parts by mass of 5-n-hexyl stupid phenol (manufactured by Wako Pure Chemical Industries Co., Ltd.) was added. Further, the solution was dissolved, and further, 3 parts by mass of the subsequent auxiliary solution (D-1) obtained in Reference Example 6 was added, and 6 parts by mass of ruthenium trimellitate (trade name: TRIAM705 and Wako Pure Chemical Industries, Ltd.) was added. After making a solution and making it dissolved, it is filtered using a filter of 1 μη! A photosensitive resin composition was obtained. [Table 1] (Α) alkali-soluble resin (Β) photosensitive diazonaphthoquinone compound (C) organic solvent Example 11 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of γ-butyrolactone Example 12 Ρ- 2 100 parts by mass of PAC-1 20 parts by mass of γ-butyrolactone Example 13 Ρ-3 100 parts by mass of PAC-120 parts by mass of γ-butyrolactone Example 14 Ρ-4 100 parts by mass of PAC-120 parts by mass γ- Butyrolactone Example 15 Ρ-5 100 parts by mass of PAC-120 parts by mass γ-butyrolactone 141019.doc • 83· 201005008 Example 16 P-6 100 parts by mass of PAC-1 20 parts by mass of γ-butyrolactone Example 17 P-7 100 parts by mass of PAC-1 20 parts by mass of γ-butyrolactone Example 18 P-8 100 parts by mass of PAC-1 20 parts by mass of γ-butyrolactone Example 19 P-9 100 parts by mass of PAC- 1 20 parts by mass of γ-butyrolactone Example 20 P-10 100 parts by mass of PAC-1 20 parts by mass of γ-butyrolactone Example 21 P-1 100 parts by mass of PAC-1 12 parts by mass of γ-butyrolactone Example 22 P-1 100 parts by mass of PAC-1 26 parts by mass of γ-butyrolactone Comparative Example 6 P-11 100 parts by mass of PAC-1 20 parts by mass ΝΜΡ Comparative Example 7 P-12 100 parts by mass of PAC-1 20 parts by mass ΝΜΡ Comparative Example 8 P-13 100 parts by mass PAC-1 20 mass ΝΜΡ Comparative Example 9 P-14 100 parts by mass of PAC-1 20 parts by mass ΝΜΡ Comparative Example 10 P-15 100 parts by mass of PAC-1 20 parts by mass of γ-butyrolactone &lt; Glass transfer of cured film of photosensitive resin composition Measurement of Temperature (Tg)&gt; The photosensitive resin compositions of Examples 11 to 22 and Comparative Examples 6 to 10 were applied to 6 利用 by a spin coater (Clean Track Mark 7 manufactured by Tokyo Electronics Co., Ltd.). On the wafer, after drying at 130 ° C for 180 seconds, a temperature-increasing tank (VF200B manufactured by Koyo Thermo System Co., Ltd.) was used, and heated at 320 ° C for 1 hour under a nitrogen atmosphere to obtain a film thickness of 1 Torr. It is a thermal curing film. The cured film was cut into a width of 3 mm, and immersed in a dilute aqueous solution of hydrofluoric acid for one night. The film was peeled off and dried, and a TMA apparatus (TMA-50 manufactured by Shimadzu Corporation) was used, and a nitrogen flow rate of 50 ml/min was used. The glass transition temperature was measured under the conditions of a temperature rising rate of 10 ° C /min. The results are shown in Table 1 below. 141019.doc •84· 201005008 [Table 2] i-line exposure sensitivity (mJ/cm2) Tg(0C) development initial film thickness margin (μπι) Solubility of PGME Example 11 225 265 1.2 〇Example 12 225 265 1.2 〇 Example 13 250 265 1.2 〇 Example 14 275 260 1.2 〇 Example 15 250 260 1.2 〇 Example 16 300 270 0.6 〇 Example 17 275 265 0.8 〇 Example 18 325 280 0.6 〇 Example 19 325 285 0.6 〇 Implementation Example 20 300 305 0.8 〇 Example 21 250 265 0.8 〇 Example 22 300 265 0.6 〇 Comparative Example 6 550 180 0.2 X Comparative Example 7 475 220 0.4 〇 Comparative Example 8 500 210 0.4 X Comparative Example 9 Unable to observe 285 Unable to observe X Comparative Example 10 | 450 297 0.4 〇

&lt;Evaluation of photosensitive resin composition&gt; (1) Evaluation of patterning property Using a spin coater (Clean Track manufactured by Tokyo Electronics Co., Ltd.)

Mark 7) The photosensitive resin composition was applied onto a 6-inch wafer and dried at 130 ° C for 180 seconds to obtain a coating film having a thickness of 11.0 μm. The coating film was exposed by an i-line stepper-exposure machine (NSR2005i8A manufactured by Nikon Corporation) through a reticle and changing the exposure amount stepwise at 25 mJ/cm2. The development time was adjusted by using 2.38% of TMAH aqueous solution (AZ3 00MIF manufactured by Clariant Japan Co., Ltd.) at 23 ° C in such a manner that the film thickness after development reached 9.3 μm (remaining film rate at development was 85%). The wafer was developed and rinsed with pure water for 15 seconds to obtain a 141019.doc -85-201005008 relief pattern. The embossed pattern was observed with a microscope, and the minimum exposure amount by which the 3.5 μπι square embossed pattern of the exposed portion was dissolved was defined as the sensitivity, and the results are shown in Table 2. Furthermore, the film thickness 11 () before the development is called the film is added every time, and the coating film is exposed to a minimum exposure of 25 mj/em2 when the initial film thickness is n G (four). The time constant is the development time obtained when the initial film thickness is 11.G μηη, and development is performed to obtain a film thickness of 3 5 μηι square relief pattern when the film thickness is increased by 11.0 μπι. degree. With respect to the photosensitive resin composition of Comparative Example 9, development was carried out with a minimum development time of the developing machine, that is, 9 seconds, and the dissolution rate of the unexposed portion was extremely fast, and adjustment was impossible so that the film thickness after development reached 93 μm, and as a result, it was not obtained. The desired relief pattern. The reason for this is that in the unexposed portion, the naphthalene azide contained in pAC_ i does not exhibit the effect of inhibiting dissolution in the alkali-soluble resin. As a result, the difference in the dissolution rate between the unexposed portion and the exposed portion is not obtained. Comparative Examples 6, 7, 8, and 1 Although the desired pattern of 3 5 μm was obtained, the sensitivity required to obtain the pattern was lower. In Examples u to 22, a relief pattern having a high film thickness was obtained when the film was treated with the same development time and the same exposure amount. &lt;Solubility of the relief pattern in the propylene glycol monomethyl ether after development&gt; The photosensitive resin composition prepared in Examples 11 to 22 and Comparative Examples 6 to 10 was partially formed in the embossed pattern after development. The test was carried out by immersing in propylene glycol monomethyl ether (also referred to as PGME (propylene glycol mono methyl ether)) for 5 minutes at room temperature to confirm whether or not the developed coating film was dissolved. The results were 141019.doc -86· 201005008, and the examples 11 to 22 were cleanly dissolved and removed. The comparative examples were not dissolved except for 7 and 1 Å, and the rest were within 5 minutes. &lt;Preparation of hardened relief pattern&gt; Using a temperature-raising oven (VF200B manufactured by Koy〇 Therm〇systern Co., Ltd.), the iridium wafer with the relief pattern obtained in Example i^22 was placed under a nitrogen atmosphere. , 320. (: heating for 1 hour, and obtaining a hardened relief pattern having a film thickness of 5 μη. The shape of the relief pattern maintains the developed pattern, and the pattern shape is excellent. This is because the polymer end is subjected to 5_norbornic anhydride. Effect of capping. <Evaluation of the best (C) organic solvent> Using the polymer oxime obtained in Example 1 instead of GBL, dissolved in the organic solvent not shown in Table 3 below, and in addition to the examples In the same manner, a positive photosensitive resin was produced and the patterning property was evaluated. At this time, the flatness of the coating film before development was determined. Determine the difference between the maximum film thickness and the minimum film thickness at 7 points on the diameter of the 6-material wafer, and divide it by the film thickness of 7 points (defined as surface smoothness). In Table 3. It can be considered that the smaller the value, the better the surface smoothness. In the case of the propionate or the acetonide of the acetic acid of Example 27, the coating film was formed into a star shape due to the dissolution of the solvent during the coating process, and the coating film was uniformly coated at At仏*^^禾月t*. On the wafer. Further, the test mixture was allowed to stand under air and left at room temperature for 2 weeks to determine the viscosity change of the composition.杳· Λ: ϊ 1 λ Semi-Examples 24 and 25, dimethyl ethanoamine, if after 2 weeks, +, due to the influence of moisture in the milk, white turbidity in Examples 26, 27, In 28, the viscosity of the composition increased. The GBL of Example 23 is superior in terms of flatness, sensitivity, film thickness margin, and stability of the coating film 141019.doc •87·201005008. [Table 3] (C) Minimum exposure amount of organic falling agent (mJ/cm2) Development initial film thickness margin (μπι) Surface smoothness composition viscosity change rate Example 23 GBL 225 1.2 0.0113 +1.2% Example 24 ΝΜΡ 325 0.8 0.0242 +0.8% Example 25 Dimethylacetamide 350 1.0 0.0293 +2.8% Example 26 Cyclohexanone 350 0.8 0.0946 + 15.3% Example 27 Cannot be evaluated for the inability to evaluate the inability to measure +111% Example 28 The ester could not be evaluated, the evaluation could not be evaluated, the evaluation could not be evaluated, and the evaluation of the optimum (D) alkoxydecane compound was carried out in the alkali-soluble resin solution (P-1) obtained in each of the above Example 1, relative to the alkali solubility. 100 parts by mass of the resin resin, and after dissolving 20 parts by mass of the photosensitive diazonaphthoquinone compound PAC-1 obtained in Reference Example 5, 4 parts by mass of 5-n-hexyl resorcinol was dissolved (Wako Pure Chemical Industries Co., Ltd.) According to the combination of the following Table 4, 30 parts by mass of the auxiliary solution obtained in Reference Examples 6 to 9 or 6 parts by mass of a commercially available oxime coupling agent was added, and after dissolution, 1 μm was used. The transitioner has been , To obtain a positive photosensitive resin composition. [Table 4] (Α) alkali-soluble resin (Β) photosensitive diazonaphthoquinone compound (D) alkoxy decane compound Example 29 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of D-1 solution 30 parts by mass Example 30 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of D-2 solution 20 parts by mass of D-3 solution 10 parts by mass Example 31 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of D-3 solution 30 mass Part 32: Ρ-1 100 parts by mass of PAC-1 20 parts by mass of D-4 solution 30 parts by mass Example 33 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of Ν-phenyl-γ-aminopropyl three曱oxydecane (trade name ΚΒΜ573, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass 141019.doc -88- 201005008 Example 34 P-1 100 parts by mass of PAC-1 20 parts by mass of 3-mercaptopropyltrimethoxy Base decane (trade name Sila-Ace S810, manufactured by Chisso Co., Ltd.) 6 parts by mass of Example 35 P-1 100 parts by mass of PAC-1 20 parts by mass of N-(3-triethoxydecylpropyl)urea ( Azmax Co., Ltd., trade name SIU9055.0) 6 parts by mass of Example 36 P-1 100 parts by mass of PAC-1 20 parts by mass of 3-(m-aminophenoxy)propyltrimethoxydecane (Azmax shares) Manufactured under the trade name SLA0598.0) 6 parts by mass of Example 37 P-1 100 parts by mass of PAC-1 20 parts by mass of 2-(tridecyloxy sulphate) bismuth (manufactured by Azmax Co., Ltd.) Product name: SIT8396.0) 6 parts by mass of Example 38 P-1 100 parts by mass of PAC-1 20 parts by mass of γ-aminopropyltriethoxydecane (trade name TSL8331, manufactured by Toshiba Organic Co., Ltd.) 6 parts by mass Example 39 P-1 100 parts by mass of PAC-1 20 parts by mass of γ-glycidoxypropyltriethoxydecane (trade name: 403, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass of Example 40 P-1 100 mass Part by weight of PAC-1 20 parts by mass of γ-methacryloxypropyltriethoxydecane (trade name: 503, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass of Example 41 P-1 100 parts by mass of PAC-1 20 mass Vinyl triethoxy decane (trade name: 1003, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts by mass of Example 42 P-1 100 parts by mass of PAC-1 20 parts by mass, not added to the positive-type photosensitive resin composition, The patterning property evaluation was carried out in the same manner as in Example 11, and the exposure with a minimum exposure amount of 100 mJ/cm2 was observed. The pattern of the quantity, the length of the observation is 1 cm: 1 line and the gap are arranged in a pattern of 5, and the line and gap pattern of the minimum size of 5 are completely defined as the minimum follow-up pattern, and the pattern is followed by the development. Sexual comparison. The results are shown in Table 5 below. In this case, the development of the smaller-sized line and the gap is good. 141019.doc 89- 201005008 [Table 5] Necessary minimum exposure amount (mJ/cm2) Minimum exposure amount +100 mJ/cm2 minimum follow-up pattern (μπι) High-pressure cooking test 100-hour tape tensile test Example 29 225 0.5 100 Example 30 225 3 100 Example 31 225 2 100 Example 32 225 2 100 Example 33 225 0.5 100 Example 34 225 1 100 Example 35 225 2 100 Example 36 225 1 100 Example 37 225 1 100 Example 38 Evaluation of varnish became black 100 Example 39 Gelled material could not be evaluated Cannot be filtered Unevaluable Example 40 225 18 0 Example 41 225 26 0 Example 42 225 90 0 In Examples 29 to 37, there were 3 micron or less The pattern follows. Further, the aliphatic amine group of Example 38 or the glycidyl group of Example 39 produced a gel during the production of the composition or made the varnish black, which was not evaluated. Further, the positive photosensitive resin composition obtained in the above Examples 29 to 42 was applied onto a 6-inch wafer at 130° by a spin coater (Clean Track Mark 7 manufactured by Tokyo Electronics Co., Ltd.). After drying for 180 seconds at C, a heat-resistant oven (VF200B manufactured by Koyo Thermo System Co., Ltd.) was used, and heated at 320 ° C for 1 hour under a nitrogen atmosphere to obtain a heat-resistant cured film having a film thickness of 1 〇.〇μηη. . After the sample formed by forming the cured film was treated with a pressure cooker (131 ° C, 3.0 atm) for 100 hours, a utility knife was formed by a grid test (JIS K5400) in such a manner as to form 100 squares of 1 mm square. (cutter knife) engraved 141019.doc -90- 201005008 mark, attached to the cellophane (registered trademark) tape from the top and peeled off, and the number is not attached to the sericin (registered trademark) tape and remains. 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 quantity, the better the adhesion. In Examples 29 to 37, the adhesion of the pattern after development, the adhesion to the wafer after thermal curing, and the storage stability of the photosensitive resin composition were satisfactory, which was preferable. &lt;(E) Evaluation of Compound by Cross-Reaction Reaction by Heat&gt; Φ In the alkali-soluble resin solution (P-1) obtained in each of the above Examples 1, 100 parts by mass of the pure component of the alkali-soluble resin resin After dissolving 20 parts by mass of the photosensitive diazonaphthoquinone compound PAC-1 obtained in Reference Example 5, 4 parts by mass of 5-n-hexylresorcinol (manufactured by Wako Pure Chemical Industries Co., Ltd.) was dissolved. 30 parts by mass of the subsequent auxiliary solution obtained in Reference Example 6 was added, and the compound which was subjected to the crosslinking reaction by heat was dissolved according to the combination of the following Table 6, and then filtered using a filter of 1 μm to obtain a positive A photosensitive resin composition. Θ [Table 6] (Α) alkali-soluble resin (Β) photosensitive diazonaphthoquinone compound (E) Compound which undergoes crosslinking reaction by heat Example 43 Ρ-1 100 parts by mass of PAC-120 parts by mass CL-1 10 parts by mass of Example 44 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-2 10 parts by mass of Example 45 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-3 10 parts by mass of Example 46 Ρ- 1 100 parts by mass of PAC-120 parts by mass of CL-4 10 parts by mass of Example 47 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-5 10 parts by mass of Example 48 Ρ-1 100 parts by mass of PAC-1 20 mass Part CL-6 10 parts by mass Example 49 Ρ-1 100 parts by mass PAC-120 parts by mass CL-7 10 parts by mass Example 50 Ρ-1 100 parts by mass PAC-1 20 parts by mass CL-8 10 parts by mass Example 51 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-9 10 parts by mass 141019.doc •91 · 201005008 Example 52 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-10 10 parts by mass of Example 53 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-11 10 parts by mass of Example 54 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-12 10 parts by mass of Example 55 Ρ-1 100 parts by mass of PAC- 1 20 parts by mass of CL-13 10 mass Example 56 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-4 5 parts by mass Example 57 Ρ-1 100 parts by mass of PAC-1 20 parts by mass of CL-4 20 parts by mass Example 58 Ρ-1 100 mass PAC-1 20 parts by mass of CL-4 30 parts by mass of Example 59 Ρ-1 100 parts by mass of PAC-1 20 parts by mass No patterning was carried out in the same manner as in Example 11 except that the positive photosensitive resin composition was not added. Characteristic evaluation. The results are shown in Table 7 below. The thus-attached patterned silicon wafer was heated at 320 ° C for 1 hour in a nitrogen atmosphere using a temperature-raising oven (VF200B manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a heat-resistant cured film. After measuring the film thickness of the heat-resistant cured film of the patterned wafer, the wafer was immersed in a bath filled with a photoresist stripping solution TOK105 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 40 ° C for 30 minutes. After washing with pure water, the film thickness was measured, and the residual film ratio was measured. Then observe the state of the pattern. The results are shown in Table 7. [Table 7] (Ε) Compound glass transition temperature by heat crosslinking reaction CC) Chemical resistance test residual film ratio (%) Observe the change in viscosity of the chemical resistance test pattern after standing for 4 weeks at room temperature (%) Example 43 CL-1 10 parts by mass 264 100% No problem 18% Example 44 CL-2 10 parts by mass 261 100% No problem 7% Example 45 CL-3 10 parts by mass 268 100% No problem 8% Implementation Example 46 CL-4 10 parts by mass 269 100% No problem 9% Example 47 CL-5 10 parts by mass 270 100% No problem 6% Example 48 CL-6 10 parts by mass 265 100% No problem 5% Example 49 CL-7 10 parts by mass 264 100% No problem 5% Example 50 CL-8 10 parts by mass 262 100% No problem 5% Example 51 CL-9 10 parts by mass 259 100% No problem 5% Example 52 CL- 10 10 parts by mass 264 100% No problem 5% Example 53 CL-11 10 parts by mass 262 100% No problem 8% Example 54 CL-12 10 parts by mass 269 100% No problem 5% 141019.doc -92- 201005008 Example 55 CL-13 10 parts by mass 268 100% No problem 19% Example 56 CL-4 5 parts by mass 265 100% No problem 7% Example 57 CL-4 20 parts by mass 264 100% No problem 6% Example 58 CL-4 30 parts by mass 262 100% No problem 14% Example 59 252 98% not cracked 5% The glass of the cured film of the positive photosensitive resin composition was measured in the same manner as in Example 11 Transfer temperature (Tg). The results are shown in Table 7. Further, the rate of change in viscosity after each photosensitive resin composition was allowed to stand at room temperature for 4 weeks was measured. The results are also shown in Table 7. In Examples 43 to 58, the glass transition temperature φ was higher than that of the non-addition of Example 59, and the chemical resistance was also improved, which was preferable. The "(E) compound which undergoes crosslinking reaction by heat" in Table 7 is shown below. [Chem. 80] The trade name of Nikalac MW390 manufactured by CL-1 Sanhe Chemical Co., Ltd.

HjCOHjC, /C^OCHj

H3C〇H,C^ HjCOHiC n/CH2〇CH, CH2OCH3

CL-2 Sanwa Chemical Co., Ltd. Manufactured under the trade name Nikalac MX290 if h3coh2c- nh-c-nh-ch2och3 [Chemical product] CL-3 Sanwa Chemical Co., Ltd. manufactured under the trade name Nikalac MX280 and H3COH2 , n 八 N ^CH2〇CH3 CHjO 〇CH3 -93- 141019.doc 201005008 [Chem. 83] CL-4 Sanwa Chemical Co., Ltd. manufactured under the trade name Nikalac MX270 NN Μ h3coh2c into ch2och&gt;

N N h3coh2c' 丫 W)CH3 o [Chem. 84]

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

[化85]

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

OH

[化86]

CL-7 is a trade name of DMOM-PC manufactured by Honshu Chemical Industry Co., Ltd.

HjCOHiC

[Chem. 87] 2,2-bismethoxymethylbiphenyl manufactured by Tokyo Chemical Industry Co., Ltd. ch3-o-ch2

Ch2-o-ch3 141019.doc • 94· 201005008 [Chemical 88] CL-9 Maruzon Petrochemical Industry Co., Ltd. trade name baNI_x

[Chem. 89] CL-10 Maruzon Petrochemical Industry Co., Ltd. manufactured under the trade name bani_m

0 0 [Chemical 90] CL-U East Asia Synthetic Co., Ltd. trade name OXT-121

(where nl = an integer from 1 to 3)

[Chem. 91] CL-12 East Asia Synthetic (Stock) manufactured under the trade name 〇χτ_221

[Chem. 92] 2,2-bis(4-glycidoxyphenyl)propane manufactured by Tokyo Chemical Industry Co., Ltd.

O-ch2 141019.doc .95-201005008 &lt;(F) is 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. (Evaluation of at least one of the compounds) In the alkali-soluble resin solution (P-1) obtained in each of the above-mentioned Example 1, the reference substance 5 was dissolved in 14 parts by mass based on 100 parts by mass of the pure component of the alkali-soluble resin resin. After the photosensitive diazonaphthoquinone compound PAC-1 obtained in the above, 30 parts by mass of the subsequent auxiliary solution obtained in Reference Example 6, 8 parts by mass of CL-8, and 10 parts by mass of CL-9, 6 were dissolved. After a mass part of methoxyphenylacetic acid, according to the combination shown in Table 8 below, a compound selected from the group consisting of an acrylate compound, a methyl propyl phthalate compound, a compound containing a propyl group, a compound containing a methoxy group, At least one of the compounds consisting of the phenyl ester compound is subjected to a transition using a filter of 1 μm to obtain a positive photosensitive resin composition. [Table 8] (Α) alkali-soluble resin (Β) photosensitive diazonaphthoquinone compound CF) Compound Example 60 Ρ-1 100 parts by mass of PAC-1 14 parts by mass F-1 5 parts by mass Example 61 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of F-1 10 parts by mass of Example 62 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of F-1 20 parts by mass of Example 63 Ρ-1 100 parts by mass of PAC-1 14 mass Part F-2 5 parts by mass of Example 64 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of F-3 5 parts by mass of Example 65 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of F-4 5 parts by mass Example 66 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of F-4 10 parts by mass of Example 67 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of F-5 5 parts by mass of Example 68 Ρ-1 100 parts by mass PAC-1 14 parts by mass F-6 5 parts by mass Example 69 Ρ-1 100 parts by mass PAC-1 14 parts by mass F-7 5 parts by mass Example 70 Ρ-1 100 parts by mass PAC-1 14 parts by mass F- 7 10 parts by mass of Example 71 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of F-8 pentaerythritol triacrylate 5 parts by mass Example 72 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of F-8 pentaerythritol triacrylate Ester 10 parts by mass 141019.doc -96- 201005008 Example 73 P-1 100 parts by mass of PAC-1 14 parts by mass No Example 74 P-1 100 parts by mass of PAC-1 20 parts by mass No such positive photosensitive resin composition was used, and the same procedure as in Example 11 was carried out. Evaluation of patterning characteristics. The results are shown in Table 9 below. Further, the development time required at this time is also shown in Table 9. The "(F) compound" in Table 8 is shown below. [Chem. 93] F-1 and the purely medicinal product company's brand name finished product TRIAM705 Ο ❿ -

^ II II 〇 〇 [Chem. 94] FTAM 805 manufactured by F-2 Wako Pure Chemical Industries Co., Ltd.

[Chem. 95] F-3 and the purely pharmaceutical company made by the famous chemical product TRIAM501 --- [Chem. 96]

F-4 Brand name manufactured by Shin-Nakamura Chemical Industry Co., Ltd. 4EG 141019.doc -97- 201005008 [Chem. 97]

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

(wherein n2 is an integer of 1 to 20, and the average value thereof is 9) [Chem. 98] F-6 Trade name, 1,3,5-trimethoxybenzene, manufactured by Tokyo Chemical Industry Co., Ltd.

OCHi [Chem. 99] F-7 manufactured by Tokyo Chemical Industry Co., Ltd.

[Table 9] Minimum exposure amount of i-line exposure (mJ/cm2) Necessary development time (seconds) Development initial film thickness margin_) Example 60 225 60 1.2 Example 61 175 74 1.2 Example 62 175 85 1.4 Example 63 200 58 1.4 Example 64 200 55 1.6 Example 65 200 60 1.4 141019.doc -98- 201005008 Example 66 150 65 1.4 Example 67 200 74 1.4 Example 68 200 66 1.4 Example 69 175 62 1.4 Example 70 175 74 1.4 Example 71 175 58 1.4 Example 72 175 69 1.2 Example 73 300 38 0.8 Example 74 250 62 1.0 Using the temperature-raising supply box (VF200B manufactured by Koyo Thermo System), the pattern with the pattern obtained in this way The wafer 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 60 to 72 are preferred in terms of high photosensitivity and a wider film thickness margin. &lt;Evaluation of monocarboxylic acid compound&gt; In the alkali-soluble resin solution (P-1) obtained in each of the above-mentioned Example 1, 14 parts by mass of the alkali-soluble resin resin pure component was dissolved, and Reference Example 6 was dissolved. After the photosensitive diazonaphthoquinone compound PAC-1 obtained in the above, 30 parts by mass of the subsequent auxiliary solution obtained in Reference Example 6, 6 parts by mass of CL-8, and 8 parts by mass of CL-9, 10 were dissolved. After the F-1 of the above-mentioned (F) compound, a monocarboxylic acid compound was added and the mixture was filtered through a filter of 1 μm to obtain a positive photosensitive resin composition. [Table 10] (Α) alkali-soluble resin (Β) photosensitive diazonaphthoquinone compound (g) mono-hectoric acid compound Example 75 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of citronellic acid 5 parts by mass Example 76 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of citronellic acid 10 parts by mass Example 77 Ρ-1 100 parts by mass of PAC-1 14 parts by mass of citronellic acid 20 parts by mass Example 78 Ρ-1 100 parts by mass of PAC -1 14 parts by mass of decyloxyphenylacetic acid 5 parts by mass 141019.doc -99-201005008 Example 79 P-1 100 parts by mass of PAC-1 14 parts by mass of decyloxyphenylacetic acid 10 parts by mass Example 80 P- 1 100 parts by mass of PAC-1 14 parts by mass of m-benzoic acid 5 parts by mass Example 81 P-1 100 parts by mass of PAC-1 14 parts by mass of m-toluic acid 10 parts by mass Example 82 P-1 100 parts by mass of PAC -1 14 parts by mass of acetic acid 5 parts by mass Example 83 P-1 100 parts by mass of PAC-1 14 parts by mass of acetic acid 10 parts by mass Example 84 P-1 100 parts by mass of PAC-1 14 parts by mass not added for the positive type The photosensitive resin composition was evaluated for patterning characteristics in the same manner as in Example 11. These results are shown in Table 11 below. Further, the development time required at this time is also shown in Table 11. [Table 11] (g) Minimum exposure amount (mJ/cm) of single-line exposure of single-repulsive compound i. Development time (seconds) Development initial film thickness margin (μιη) Example 75 5 parts by mass of citronellic acid 175 64 1.4 Implementation Example 76 10 parts by mass of citronellic acid 175 55 1.4 Example 77 20 parts by mass of citronellic acid 175 49 1.4 Example 78 5 parts by mass of methoxyphenylacetic acid 175 62 1.4 Example 79 10 parts by mass of decyloxyphenylacetic acid 175 54 1.4 Example 80 Indolephthalic acid 5 parts by mass 175 58 1.4 Example 81 Anthraquinonecarboxylic acid 10 parts by mass 175 48 1.4 Example 82 Acetic acid 5 parts by mass 250 66 1.0 Example 83 Acetic acid 10 parts by mass 250 60 1.0 Example 84 No addition of 250 69 1.0 The thus-added patterned ruthenium wafer was heated at 320 ° C for 1 hour using a temperature-raising oven (VF200B manufactured by Koyo Thermo System Co., Ltd.) to obtain retention. A heat-resistant cured film having a pattern shape after development. Examples 75 to 8 1 are preferred in terms of high sensitivity and a wider film thickness margin. (Preparation of Negative Photosensitive Resin Composition) <Examples 85 to 94, Comparative Examples 11 to 15> According to the combination of Table 12 below, each of Examples 1 to 10 and Comparative Example 141019.doc • 100 - 201005008 In the alkali-soluble resin solution (Ρ-1 to P-15) obtained in 1 to 5, 5 parts by mass of 2-(2-() which is an acid-producing compound (PAG) by irradiation of active light is dissolved. 4-methylphenylsulfonyloxyimido)-2,3-dihydrothiophene-3-ylidene-2-(2-mercaptophenyl)acetonitrile (Irgacure PAG121, manufactured by Ciba Japan Co., Ltd.), 30 parts by mass of a CL-4 alkoxythiolated urea resin which is a compound which can be crosslinked by the action of an acid (No. MX-270, manufactured by Sanwa Chemical Co., Ltd., trade name Nikalac, monomer 95 ° /. In the above, 30 parts by mass of the subsequent auxiliary solution D-1 obtained in Reference Example 7 was further added, and after it was dissolved, φ was filtered through a filter of 1 μm to obtain a negative photosensitive resin composition. [Table 12] (Α) Alkali-soluble resin (Η) Compound which can generate an acid by irradiation with active light (I) Compound which can be crosslinked by an action of an acid (D) Alkoxydecane compound (C) Organic solvent Example 85 Ρ-1 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass of γ-butyrolactone Example 86 Ρ-2 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass D-1 solution 30 parts by mass γ-butyrolactone Example 87 Ρ-3 100 parts by mass PAG 5 parts by mass CL-4 30 parts by mass D-1 solution 30 parts by mass γ-butyrolactone Example 88 Ρ-4 100 Parts by mass PAG 5 parts by mass CL-4 30 parts by mass D-1 solution 30 parts by mass γ-butyrolactone Example 89 Ρ-5 100 parts by mass PAG 5 parts by mass CL-4 30 parts by mass D-1 solution 30 parts by mass Γ-butyrolactone Example 90 Ρ-6 100 parts by mass PAG 5 parts by mass CL-4 30 parts by mass D-1 solution 30 parts by mass γ-butyrolactone Example 91 Ρ-7 100 parts by mass PAG 5 parts by mass CL -4 30 parts by mass of D-1 solution 30 parts by mass of γ-butyrolactone Example 92 Ρ-8 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass of γ-butyrolactone Example 93 Ρ -9 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass of γ-butyrolactone 141019.doc • 101 · 201005008 Example 94 Ρ-10 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass of γ-butyrolactone Comparative Example 11 Ρ-11 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass ΝΜΡ Comparative Example 12 Ρ-12 100 Quality Part by weight PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass ΝΜΡ Comparative Example 13 Ρ-13 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass ΝΜΡ Comparative Example 14 Ρ -14 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass ΝΜΡ Comparative Example 15 Ρ-15 100 parts by mass of PAG 5 parts by mass of CL-4 30 parts by mass of D-1 solution 30 parts by mass γ - Butyrolactone &lt;Evaluation of Negative Photosensitive Resin Composition&gt; (Evaluation of Patterning Characteristics) The negative photosensitive resin compositions obtained in the above Examples 85 to 94 and Comparative Examples 11 to 15 were used. It was spin-coated on a 6-inch wafer and baked on a hot plate at 110 ° C for 3 minutes to obtain a film having a thickness of about 15 μm. The film was exposed by means of an i-line stepper-exposure machine (manufactured by Nikon Corporation, NSR2005i8A) through a mask to change the exposure amount stepwise. The exposed wafer was exposed to light at 120 ° C for 3 minutes, baked, and developed using a 2.38% aqueous solution of TMAH (AZ300MIF manufactured by Clariant Japan Co., Ltd.), followed by rinsing with deionized water to obtain a relief. pattern. The relief pattern was observed under a microscope to maintain a film thickness of about 90 °/ under the exposed area. The exposure amount of the portion is defined as the sensitivity (minimum exposure amount), and the via hole size in which the square relief pattern of the unexposed portion is completely dissolved and removed is defined as the resolution. The results are shown in Table 13 below. Further, when the initial film thickness is increased from 0.2 μm to 0.2 μm each, the minimum exposure amount and development time obtained when the initial film thickness is 15 μm are fixed, and when the lithography is evaluated, The film thickness for development is 141019.doc -102- 201005008 degrees. The results are shown in Table 13 below. In Examples 85 to 94, compared with Comparative Examples 11 to 15, it was highly sensitive and was superior in terms of a wide film thickness margin. Table 13] Minimum exposure amount (mJ/cm2) Resolution (μιη) Development initial film thickness margin (μηι) Example 85 400 10 1.6 Example 86 400 10 1.6 Example 87 400 10 1.6 Example 88 375 10 1.6 Example 89 375 12 1.6 Example 90 375 12 1.6 Example 91 400 10 1.6 Example 92 425 12 1.6 Example 93 475 10 1.6 Example 94 475 12 1.6 Comparative Example 11 550 18 0.6 Comparative Example 12 550 18 0.6 Comparative Example 13 600 20 0.6 Comparative Example 14 650 18 0.6 Comparative Example 15 550 18 0.8

[Industrial Applicability] The photosensitive resin composition of the present invention can be preferably used in the fields of a protective film for a semiconductor, an interlayer insulating film, a liquid crystal alignment film, and the like. 141019.doc -103-

Claims (1)

201005008 VII. Patent application scope: 1. An alkali-soluble resin which has a structure represented by the following general formula in the molecule: Table [Chemical Formula 1] ΟΗ ο 0 NH-XrNH~C-ZnC- (1) OH Wherein 'Χι denotes a divalent organic group represented by the formula (2) of a tetravalent organic group containing a halogen atom: [Chemical 2] Ζι denotes the following (2) (In the case where there are a plurality of cases of 1^ and 1^2, respectively, each represents a certain or a hydroxyl group, and ... and ~ represent an integer of 0 to 3), and is called an integer representing 1 to}.碱2. The alkali-soluble resin of claim 1, which has a structure represented by the following formula (3) in the molecule: wherein X represents a tetravalent organic group containing a halogen atom, \ represents a tetravalent organic group which does not contain a dentate atom, Z1 represents an valence organic group represented by the above formula (2), Ζ2 represents a divalent organic group having a carbon number of 3 to 40, and m represents an integer of 1 to 200. , call, call, and call are respectively independent of 〇~2(10) 141019.doc 201005008 number, here, when (mi+ni2+m3+m4) is set to 100%, mi molar ratio + + More than 25%}. 3. The alkali-soluble resin according to claim 1 or 2, wherein X of the formula (1) or (3) is the following structure: [Chemical 4] 4. The alkali-soluble resin of claim 2, wherein the &amp; described in the formula (3) is the following structure: [Chemical 5] 5. The alkali-soluble resin of claim 2, wherein the oxime described in the formula (3) ψ叱 7 τ is selected from the group consisting of the following structural formula (4). [Chem. 6] In the formula, L5 is selected from the monovalent group of the following structural formula (5) [Chemical 7] NH-C-0-Le (s) 141019.d〇c 201005008 6· (Formula 、, L6 represents a monovalent alkyl group having a carbon number of 1 to 4)}. The alkali-soluble resin of the first or second aspect, wherein the formula (1) or the formula (3) has at least one terminal group of the group consisting of the following structural formula (6): 8] (6) Ο HOOCT sensitizing J. raw resin composition containing (10) parts by mass of (4) an alkali-soluble resin containing the alkali-soluble resin of claim 1 or 2, comprising 1:100 parts by mass of (Β) photosensitive diazonium Naphthoquinone compound. The positive photosensitive resin composition of the present invention, which further comprises 100 to 2000 parts by mass of the (c) organic solvent. 9. The positive photosensitive resin composition of claim 7 or 8, wherein (B) the photosensitive diazonium compound is selected from the group consisting of a poly-based compound of the formula (7): a group consisting of azide_4_ successive acid vinegar and 1,2-naphthoquinonediazide-5-sulfonate of the polyamino group compound: [Chemical 9] 141019.doc 201005008 (c) Organic solvent ι〇· The positive photosensitive resin composition of claim 8 is γ-butyrolactone. 11. The positive photosensitive resin composition of claim 7 〇·〇 1 to 20 parts by mass of the (D) alkoxydecane compound. Further, it further comprises 12. The positive photosensitive resin composition of claim U, wherein (9) the alkoxylated compound is selected from the group consisting of compounds represented by the following general formulae (8) to (15): ] In the formula, Χι and X2 represent a divalent organic group 'parent 3 and a monovalent organic group, and s represents an integer of 0 to 2}; [Chem. 11] (9) In the formula, X7 and X9 represent a divalent organic group, X8 represents a tetravalent organic group, X5, X6, Xig and Xn represent a monovalent organic group, and s represents a total of 141~2. [Chemical 12] Xu~~Si—(〇—X15)js ^14)4 (1 0) {wherein, Χ13 represents a divalent organic group, Χ12, Χ!4 and Χΐ5 represent a monovalent organic group, and S represents An integer from 0 to 2, and t represents an integer from 0 to 5}; [Chem. 13] Ο Η II ! An N—(〇Xi9)3·5 (Xi«)s 01) {wherein, Xl6 represents -NH-R20 or -〇-R2i (here, R20, and R21 indicate that COOH is not included) a monovalent organic group; X17 represents a divalent organic group, χ18 and X19 represent a monovalent organic group, and s represents an integer of 0 to 2; [Chem. 14] HS—X22~~ Si—(0X24)3.8 (X2i)s (1 2) {wherein Xu represents a divalent organic group, Xu and Xu represent a monovalent organic group, and s represents an integer of 0 to 2}; 15] NH—X25为i—((Ο Χ«)3·ι (1 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}; 141019 .doc (14) 201005008 [Chem. 16] -Sj-(〇X32: (Xjlii :)}.s X29 represents a formula selected from the group consisting of X28, which represents a hydrogen atom or a fluorenyl group, and a divalent group: [Chem. 17] 〇〇0-C- NH—C-NH—·—NH—CO—c—CFj 〇—C— —NH—C—CF, X3〇 denotes a divalent organic group, 乂” and 32 represents an integer of the valence organic group. 'and u means an integer from 1 to 3}; [Chem. 18] • CHj — ~SOj- OU —NH—C-NH, Ο Μ —C—〇-—— 〇s means 0~2 义3 广Xm—宁i—(〇Xj6)js OC35). (15) where X33 is the same as x29 defined in general formula (14), J λ34 means 2 price $ machine base 'X35 and X36 means 1 The price is organic, and _ 儿 s Chen is not 0~2 ϋ number}. Included is a compound of the positive photosensitive resin composition of the above-mentioned item 7, which further contains (E) a compound which undergoes crosslinking reaction by heat. 14. The positive photosensitive resin composition of claim 13, wherein (E) the compound of the heat-generating crosslinking reaction is selected from the group consisting of an epoxy group, an alkoxymethyl group or an oxetane group. Compound, and double 141019.doc 201005008 A group consisting of bis-acvyl nadimide compounds. 15. The positive photosensitive resin composition of claim 7, which further comprises (1) a mass fraction selected from the group consisting of an acrylate compound, a methacrylate compound, an allyl group-containing compound, and a ruthenium-containing compound. A compound of at least one of a group consisting of an oxy group compound and a phenyl ester compound. 16. The positive photosensitive resin composition according to item 7, which further comprises an organic compound having a carboxyl group in the molecule in parts by mass (G). 17. A method of forming a hardened relief pattern, comprising: a coating step of forming a photosensitive resin composition as described in claim 7 on a substrate in the form of a coating layer; and exposing the layer Exposure; development step, elution and removal of the exposed portion by the developer; and heating step to heat the obtained relief pattern. A semiconductor device having a hardened relief pattern obtained by the method of forming the claim 17. A negative photosensitive resin composition comprising: (1) an alkali-soluble resin according to any one of claims 1 to 6, 〇 5 to 3 parts by mass (H) A compound which generates an acid by irradiation with active light, and 5 to 5 parts by mass of (I) a compound which can be crosslinked by the action of an acid. The negative photosensitive resin composition of claim 19, wherein the compound (1) is a compound having a methylol group or an alkoxymethyl group in the molecule. A method of forming a hardened relief pattern, comprising: a coating step of applying a negative photosensitive resin composition as claimed in claim 19 to a substrate; exposing the layer to exposure; and performing exposure after exposure a step of heating; 141019.doc 201005008, a step of removing the unexposed portion by a developing solution; and a heating step of heating the obtained relief pattern. A semiconductor device having a hardened relief pattern obtained by the method of forming the claim 21. 141019.doc 201005008 * * IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication. Chemical formula of the invention: OH Ο 0 II -NH-X]-NH-C-Z Plant C· OH (1) 141019.doc -2-