TW201011469A - Photosensitive resin composition - Google Patents

Abstract

Disclosed is a photosensitive resin composition which is characterized by comprising: (a) 100 parts by mass of a polyamide having a structure represented by general formula (1) [wherein each substituent and others are as defined in the scope of claims]; and (b) 1 to 100 parts by mass of a diazoquinone compound represented by general formula (2) [wherein each substituent and others are as defined in the scope of claims].

Description

[Technical Field] The present invention relates to a positive photosensitive resin composition having excellent photosensitivity and resolution, and a method for producing a highly heat-resistant embossed pattern using the same . [Prior Art] As the surface protective film or interlayer insulating film of the semiconductor element, a polyimide resin having excellent heat resistance, electrical properties, mechanical properties and the like is used. The polyimine resin is usually formed by coating a non-photosensitive polyimide precursor or a photosensitive polyimide precursor composition and then subjecting it to amination treatment. In the case where the polyimine resin must be patterned, a photosensitive polyimide intermediate composition is usually used. The reason for this is that, in the case of a photosensitive polyimide intermediate composition, after application, it is imagewise exposed by active light, and then subjected to development, heat kiln imidization or the like, whereby the polymerization can be easily formed. The quinone imine pattern can significantly shorten the steps compared to the case of using non-photosensitive styrene. However, when patterning is carried out using the photosensitive polyimide intermediate composition, an organic solvent such as fluorenylmethyl-2-pyrrolidinium must be used in a large amount as a developing solution in the developing step. However, there are problems such as the influence on the working environment and other processes in the factory. Therefore, countermeasures or technology development for developing without using an organic solvent are strongly demanded. Therefore, various proposals have been made for heat-resistant photosensitive resin materials which can be developed in a dilute alkaline aqueous solution in the same manner as the photoresist (hereinafter, see Patent Documents 1 and 2). 140314.doc 201011469 Among them, in recent years, attention has been paid to the method of water-based alkali-soluble hydroxypolyamine, such as polybenzoxazole (hereinafter also referred to as "pBO") precursor and diazonaphthoquinone (hereinafter also referred to as Photoactive components (hereinafter also referred to as "PAC") such as "DNQ" are used in combination. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. 2004-117999 (Patent Document 7) JP-A-2008-58548 SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, there are still many problems in the photosensitive alkaline developing system obtained by the method disclosed so far. In the case of using the photosensitive resin composition of DNQ, the ability to reduce the alkali solubility of the composition (dissolution inhibition) by the addition of DNQ to the alkali-soluble polymer, and the developer of the unexposed portion Patience is produced. On the other hand, in the exposed portion, DNQ was replaced with phthalic acid, and the dissolution inhibiting ability disappeared and dissolved in the developing solution. Patterning is performed by the difference in alkali solubility between the exposed portion and the unexposed portion, and in order to obtain patterning performance with high sensitivity and high residual film ratio, it is possible to sufficiently obtain the difference in solubility between the two. That is, the following high-sensitivity PAC must be used: |^ Adding pAc to dissolve 140314.doc 201011469 Extremely decisive, - Gu & ^ Shadow liquid tolerance, and other aspects, with sufficient testability in the exposure section Decomposition, while exhibiting a sufficiently small amount of light, is effective for understanding that the above-mentioned Patent Document 3 uses a developer having a solid volume and a large volume of the developing portion of the light-receiving portion as a mother core. In order to improve the non-exposure 2, if the PAC' is improved for high sensitivity,

In the case where the green resin M compound is formed, the solubility of the organic solvent is lowered, and the precipitation property is a problem. In other words, during the period in which the photosensitive (4) composition is dissolved in the organic solvent, and the photosensitive (4) composition is allowed to enter the room temperature, refrigerated or cold storage, the PAC form precipitates and is practically unusable. This photosensitive resin composition. Therefore, it is necessary to reduce the DNQ introduction rate, and it is substantially impossible to achieve high sensitivity. Further, there is a problem that the mother core of such a complicated structure is complicated in manufacturing steps such as a reaction in a multi-stage reaction at the time of synthesis, and it is difficult to perform quality management or the like due to generation of a large amount of by-products. On the other hand, the PAC of the mother core of the smaller structure as in Patent Documents 2, 5, 6, and 7 has a problem of low sensitivity. In the above, a photosensitive resin composition of PAC which satisfies the stability of lithographic performance such as sensitivity and precipitation, etc., at a high level has not been used. An object of the present invention is to provide a photosensitive resin composition, a method for producing a high heat-resistant embossed pattern using the same, and a semiconductor device having the cured embossed pattern, wherein the photosensitive resin composition exhibits high sensitivity. That is, the pattern film after patterning in the low exposure amount region is reduced by 140314.doc 201011469, the amount is small, and the resolution is excellent, and it is difficult to cause precipitation of PAC. [Means for Solving the Problem] The inventors of the present invention have focused on PAC, and have conducted efforts to develop a photosensitive resin composition that exhibits high sensitivity and high resolution of patterning performance and is difficult to extract pAC. As a result, it has been found that the above characteristics can be satisfied by using a PAC' having a specific structure, thereby completing the present invention. That is, the present invention is as follows. [1] A photosensitive resin composition comprising: U) 1 part by mass of polyamine having a structure represented by the following formula (1): [Chemical Formula 1] • HN—X, an NHC 〇_ (l) (〇H)q ΥιCo—(COOR)m (wherein X1 is a 2~4-valent organic group having 2 or more carbon atoms, and Y1 is a 2~6-valent organic having 2 or more carbon atoms; The base, P and q are each independently an integer of 0 to 4, R is a hydrogen atom or the carbon number is Μ. The organic group, the claw is an integer of 〇~2 'η is an integer of 2 to 1_ where m, P And q is not 不同 at the same time, and when both ? and 4 are 0, R is a broad base having a phenolic hydroxyl group; and (b) is a diazo brewing compound represented by the following general formula (2). : 140314.doc 201011469 [Chemical 2]

(2) In the formula, 丨, Z2 and Z3 are independent of the 碳 有机 organic base with carbon number (b), the knives are independent of 〇~4, and e is an integer of 〇~5, a plurality of q Any one is as follows: [Chemical 3]

Any one of the two bases indicated, the remainder being a hydrogen atom}. Above (b) diazonium

[2] The photosensitive resin composition of the above [1], wherein the compound is a compound represented by the following formula (3): [Chemical 4]

In the formula, any one of the plurality of Qs is determined by the following 140314.doc 201011469 [Chemical 5]

The two bases are not listed, and the rest are hydrogen atoms}. [3] The photosensitive resin composition of the above [1] or [2] wherein the (4) polyamine has a repeating unit represented by the following formula (4): [Chem. 6]

OH is a sub- 2 - NHC 〇 ~ Y2 - CO OH (4) { wherein, 2 is a tetravalent aromatic group, and ¥ 2 is a divalent aromatic group and an integer of 2 to 1 }. [4] A method for producing a hardened relief pattern, comprising the steps of: applying a photosensitive resin composition according to any one of the above [1] to [3] to a substrate;

a step of exposing or directly or ion beaming with actinic rays through a mask; a step of irradiating light, an electron beam to dissolve or remove the exposed portion or the irradiating portion; and a step of heating the obtained relief pattern. [5] A hardened relief pattern of a semiconductor device. It is obtained by the method of the above [4]. I40314.doc -8 - 201011469 [Effects of the Invention] According to the present invention, a photosensitive resin composition, a method for producing a high heat-resistant embossed pattern using the same, and a method for producing the same In the semiconductor device having the hardened relief pattern, the photosensitive resin composition exhibits high sensitivity, that is, the amount of pattern film reduction after patterning in a low exposure amount region is small, and excellent resolution, and It is difficult to cause the precipitation of PAC. [Embodiment] Hereinafter, each component constituting the photosensitive resin composition of the present invention will be specifically described. (a) Polyamine (a) Polyamine has a structure represented by the following formula (1): (Chemical Formula 7) (1) (〇H>P (OH)q HN-Xj-NHCO-Yj-C ( (C00R)m

In the formula, X! is a fluorenyl group having 2 to 4 valences having 2 or more carbon atoms, and γι is a 2 to 6 valent organic group having 2 or more carbon atoms, and p and q are each independently an integer of 〇4. R is a hydrogen atom or an organic group having a carbon number of _, and an integer 'η is an integer from 2 to 1000' wherein m'Mq is not 〇 at the same time, and when both P and q are 0, R is Phenolic hydroxyl group}. (4) Polyamine is obtained by polycondensing a diamine having a structure of X1(〇H)p with a diernic acid having a structure of Yi(〇H)q(CO〇R)m2. & A preferred fluorene has 2 to 4 valent organic groups of 2 or more and 3 G or less carbon atoms. 140314.doc 201011469 30 to 30 carbon atoms of 2 to 6 organic ‘better is 2 to 100 range, and most preferably ι has more than 2 bases. η is preferably in the range of 2 to 2 . It is preferably in the range of 3 to 50. (4) Polyamide can be used. c is heated and then dehydrated and closed to a heat resistant resin called poly (tetra) polybenzoate. Examples of the diamine having a structure of X1(0H)p (wherein ? is an integer of 〇~4) include aromatic diamine, decanediamine, and hydroxydiamine. In addition, examples of the aromatic diamine include m-phenylenediamine, p-phenylenediamine 2,4 f-p-monoamine, 3,3'-diaminodiphenyl (tetra), and 3,4,-diamine. Diphenyl ether, 4,4,-diaminodiphenyl ether, 3,3,-diaminodiphenyl sulfone, 4.4-monoaminodiphenyl sulfone, 3 4, _diamine Phenyl sulfone, 3,3,-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4,-diaminodiphenyl decane, 4,4'-di Aminodiphenyl sulfide, 3,31-diaminodiphenyl ketone, 4,4,-aminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 2,2,_ Bis(4-aminophenyl)propane, 2,2'-bis(4-aminophenyl)hexafluoropropane, uk% aminophenoxy)benzene, 1,3-bis(4-amine Benzophenoxy)benzene, anthracene, 4_bis(4-aminophenoxy) stupid, 4-methyl-2,4-bis(4-aminophenyl)-1-pentyl, 4-anthracene Base-2,4-bis(4-aminophenyl)-2-pentene, 1,4-bis(α,α-dimethyl-4-indobenzyl)benzene, iminodi-p-phenylene Diamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 4-methyl-2.4-bis(4-aminophenyl)pentane, 5 (or 6)-amino-1 -(4-aminophenyl)-1,3,3-three Base ruthenium, bis(p-aminophenyl)phosphine oxide, 4,4'-diaminoazobenzene, 4,4.-diaminodiphenylurea, 4,4'-bis(4-amine Phenyloxy)biphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl] Hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]di 140314.doc •10· 201011469 benzophenone, 4,4|-bis(4-aminophenoxy) ) 2,4,_bis[4_(α,α_dimethyl-4-amino)phenoxy]benzophenone, 4,4,_bis[4(α,α Dimercapto-4-3⁄4 base group) phenoxy]diphenyl milling, 4,4,-diaminobiphenyl, 4,4,-diaminobenzophenone, phenylindane diamine , 3,3,_dimethoxy_4,4,-diaminobiphenyl, 3,3'-dimercapto-4,4'-diaminobiphenyl, o-aniline sulfone, 2,2_ Bis(4-aminophenoxyphenyl)propane, bis(4-aminophenoxyphenyl) thio, bis(4-aminophenoxyphenyl) sulfide, hydrazine, 4-(4 amino group Phenoxyphenyl)benzene, 1,3-(4-aminophenyloxyphenyl)benzene, 9,9-bis(4-aminophenyl)anthracene, 99-bis(4-aminophenyl) 4,4,_di(3_aminophenoxy) Diphenyl sulfone, 4,4,-diaminobenzene fluorenyl aniline, and the hydrogen atom of the aromatic nucleus of the aromatic diamine are selected from the group consisting of a gas atom, a fluorine atom, a desert atom, a methyl group, and a methoxy group. A compound substituted with at least one substituent of the group t consisting of a group, a cyano group and a phenyl group. Further, in order to improve the adhesion to the substrate, decyl diamine may be selected, and as an example, bis(4-aminophenyl)dimethyl decane and bis(4-aminophenyl)tetraindole may be mentioned. Keshixi milk-fired, bis(p-aminophenyl)tetradecyl dihydrogenate, bis(γ-aminopropyl)tetramethyldioxane, L4-bis(γ-aminopropyldiazine (Alkyl)alkyl, bis(4.aminobutyl)tetradecyldioxane, bis(γ-aminopropyl)tetraphenyldioxane, and the like. Further, in order to increase the solubility of the base of polyamine, it is preferred to use a hydroxydiamine as an example, which may be exemplified by 3,3,-dihydroxybenzidine, 3,3,diamine-4,4. '_Dihydroxybiphenyl, 4,4'-diamino-3,3,-dihydroxy phenyl, 3,3,-diamino-4,4'-dihydroxydi-phenyl sulfone, 4,4 , diamino-3,3,-dihydroxydiphenylanthracene, bis(3-amino-4-hydroxyphenyl) decane, 2,2-bis(3-amino-4_hydroxyphenyl) Propane, 2,2-bis(3-aminohydroxyphenyl)hexafluoropropane, 2,2.bis (4-140314.doc 201011469 Amino-3-hydroxyphenyl) hexafluoropropane, bis(4-amine Benzyl-3-hydroxyphenyl)methane 2,2-bis(4-amino-3-hydroxyphenyl)propane, 4,4,-diamino-3,3,-dihydroxybenzophenone, 3 ,3,-diamino-4,4,-dihydroxydibenzophenone, 4,4,-diamine soil~~~-based diphenyl sulfonate, 3,3'-diamino-4,4 '-Di-based diphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, anthracene, 3-diamino-2,4-dihydroxybenzene, 1,3-diamine 4,6-dihydroxybenzene and the like. These diamines may be used singly or in combination. Among them, as a particularly good example, X! is selected from the following: [Chem. 8]

The divalent group represented by the formula YjOH^COOf^d in the above formula (1), q is an integer of 〇, and m is an integer of 0 to 2, and is exemplified by the following: 9]

140314.doc •12· 201011469

NHCO. ~0~ -(〇~ { where A is selected from -CH2-, -O-, -S-, and -C(CF3)2-f}; the base represented by: ]

COOR {wherein, R is the same as R of the above formula (1)}; or the following [Chem. 11]

ROOC COOR

Wherein R is the same as R of the above formula (1), and X3 is -(: 112-, -0-, -8-, -S02-, -CO-, -NHCO-, -C(CF3)2 -, single key or base represented by: [Chem. 12]

OH

I

-CONH-X»—NHCO-OH (wherein X4 is a base selected from the group consisting of: 140314.doc -13- 201011469 [Chem. 13]

In the above formula (1), when the ruler (4) is a hydrogen atom, the ruthenium atom or the organic group having a carbon number of 1 to 2 G, the solubility of the obtained photosensitive material is improved, but the printing is improved. ° The stability of the stable mpAc of the substance is less than 50% of the organic atomic P. Further, when the ruler is an organic base, it is preferable because the stability of the photosensitive composition obtained (4) the PAC read inhibition ability is improved, but the solubility is lowered. β is therefore an organic group, preferably having a heterogeneous radical group, especially in the case where ρ and q are both fluorene in the above formula (1), the organic group must be a fragrant light base. Examples of the preferred organic group of the material of the material (4) and (4) include a 3-hydroxybenzyl group, a 3,5-dihydroxybenzyl group and the like. The (a) polydecylamine used in the present invention is particularly preferably in the form of the following formula (in terms of excellent alkali solubility and excellent patterning properties under a thick film thereof). 4) Structure of the repeating unit represented: [Chem. 14] (4)

OH

I HN-X2_NHCO-Y2—CO- 140314.doc •14· 201011469 {wherein, X2 is a tetravalent aromatic group'. ¥2 is a divalent aromatic group, and n is an integer of 2 to 1000}. Among them, as X2, a preferred base system is exemplified by the following: [Chem. 15]

The base represented, and as I, a preferred base system can be exemplified as follows: ❹ [Chemical 16] ~ρ η〇>-〇^. ο In the general formula (4), η is preferably 2 to 2 The range of 〇〇 is better, the range is 2~1〇〇, and the best is the range of 3~50. • In the case of a polydecylamine having a repeating unit represented by the above formula (1) or (4) (hereinafter sometimes referred to simply as (a) polydecylamine), the terminal group may be bonded to a specific organic group. end. As such a capping group, for example, a group having an unsaturated bond, phthalic anhydride, succinic anhydride, 2-butene·ΐ as described in Japanese Laid-Open Patent Publication No. Hei No. Hei-5-197153 Succinic anhydride, itaconic anhydride, cyclohexyl-1,2-diphthalic anhydride, 4-methylcyclohexyl-indole-diphthalic anhydride, external _3,6-epoxy-1,2,3,6-tetra Hydrogen phthalic anhydride or the like is expected to have mechanical properties (especially the rate of 140314.doc •15·201011469) or hardened relief pattern of the coating film after heat curing. The shape is getting good. As a preferable example of such a terminal group t, the following groups are mentioned: [Chem. 17]

The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") of (a) polyguanamine used in the present invention is preferably 3,000 to 50,000. Better is 6,000~30,000. The weight average molecular weight is preferably 3,000 or more from the viewpoint of the physical properties of the hardened relief pattern. Further, from the viewpoint of analyticity, it is preferably 50,000 or less. As a developing solvent for GPC, tetrahydrofuran (hereinafter also referred to as "THF") and N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") are recommended. Further, the molecular weight was determined from a calibration curve prepared using standard monodisperse polystyrene. As standard monodisperse polystyrene, STANDARD SM-105 ° (b) diazonium compound selected from the organic solvent standard sample manufactured by Showa Denko Co., Ltd. is recommended. In the photosensitive resin composition of the present invention, it is important to contain the following 140314.doc -16- 201011469 The diazonium compound represented by the general formula (2): [Chem. 18]

(2) 1 to 10% of the organic group,

a and b are integers independently of 〇~4, c is an integer of 〇~$, and any one of the plural q is the following: [Chem. 19]

Any one of the two bases indicated is 'the rest is a hydrogen atom}. Among them, preferred are compounds represented by the following formula: [Chem. 20]

In the formula, Z!, Z2, a, b, and Q are the same as those defined in the above formula (2). Further, in terms of ease of manufacture, it is preferably represented by the following formula. Structure: 140314.doc • 17- (3) 201011469 [Chem. 21]

{wherein 'Q is the same as defined in the above formula (2)). These (b) diazonium compounds may be used singly or in combination. Further, the amount of the (b) diazonium compound to the polyamine is hWO parts by mass based on 100 parts by mass of the (a) polyamine, and the light of the resin is less than 1 part by mass. The patterning property is deteriorated. On the other hand, when it exceeds 100 parts by mass, the tensile elongation of the film formed by heat curing is remarkably lowered. The amount of the diazonium compound to be compounded is preferably from 3 to 50 parts by mass, more preferably from 10,000 parts by mass, based on 1 part by mass of the (a) polyamine. (b) The diazonium compound can be produced by subjecting a phenolic compound having a hydrogen atom of the above formula (2) as a raw material to a quinonediazide sulfonate of a hydroxyl group. In the acetalization of quinonediazide sulfonate, various sulfonic acid derivatives having a quinone naphthoquinonediazide structure may be used, preferably hydrazine, 2-naphthoquinonediazide-4-sulfonate Letter or i'2-naphthoquinone #N nitrogen_5_sulfon_. The material constitutes the original gas atom or the desert atom of the tooth of the sulphur tooth, and is usually preferably a gas atom. Therefore, as a acetating agent, it is preferred that i, 2_Cello diazide·4_石黄Brewing gas or 1,2-Caidian two stacks of gas -5 - brewing gas. Further, the esterifying agents may be used singly or in combination. This reaction is usually carried out in the presence of a dehydrogenating agent. As the de-agitating nitrogen 140314.doc -18-201011469 agent, a basic compound which can form a salt with hydrogenated hydrogen, such as an inorganic base such as sodium carbonate or sodium hydrogencarbonate, ethylamine, ethanolamine or the like, may be mentioned. An amine such as ethylamine, diethanolamine, triethylamine, triethanolamine, N,N-dimethylaniline, N,N-diethylaniline or acridine. • The dehydrogenating agent may be used singly or in combination of a plurality of types, or may be added in multiple stages. The daily reaction is usually carried out in a solvent. As a reaction solvent, it can be used to climb monooxylan, 1,4-one "defective", tetrahydrofuran, and two screams, such as ethylene glycol dimethyl ether, diethylene glycol diacetate, etc. Glycol dimethyl ether, lactones such as r butyrolactone and δ-lactone, guanamines such as N-methyl-2-pyrrolidinone, aliphatic ketones such as acetone and methyl ethyl ketone, etc. (C) Other components In the photosensitive resin composition of the present invention, a dye, a surfactant, a bonding aid for improving the adhesion to the substrate, and a dissolution may be added as needed. Promoter and cross-linking agent. The above-mentioned additives are more specifically described. Examples of the dye include methyl violet, crystal violet, malachite green, etc. • As the amount of dye added, relative to (a) polyamine 100 parts by mass, preferably 0.1 to 30 parts by mass. Further, examples of the surfactant include a non-ionic system including a glycol such as polypropylene glycol or a polyoxyethylene laurel bond or a derivative thereof. Surfactant ·, for example, wFlu〇rad (registered trademark, trade name, manufactured by Sumitomo 3M), Megafac (registered trademark, business Product name, manufactured by Dainippon Ink and Chemicals, or Lu-Im. 140314.doc • 19-201011469 Trademark, trade name, manufactured by Asahi Glass Co., Ltd.) Fluoride-based surfactant; for example, ΚΡ341 (trade name) An organic oxoxane surfactant such as dbe (trade name, manufactured by Chisso Co., Ltd.) or GLANOL (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), which is manufactured by Shin-Etsu Chemical Co., Ltd., and contains an interface activity in a photosensitive resin composition. The content of the agent is preferably from 1 to 1 part by mass based on 100 parts by mass of the (a) polyamine.

Further, examples of the auxiliary agent include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, polyvinyl methyl ether, third butyl novolac, epoxy decane, and epoxy polymer. And various decane coupling agents. Specific preferred examples of the zebra calcining agent include, for example, ice phenyl-3-aminopropyltrialkoxydecane, 3-mercaptopropyltrialkoxydecane, and 2-(dioxane). Oxidylalkylethyl)pyridine, 3-methacryloxypropyltrialkoxydecane, 3-methylpropenyloxypropyldialkoxyalkylnonane,

3-glycidoxypropyl trialkoxydecane, % glycidoxypropyl dialkoxyalkyl decane, 3-aminopropyl trialkoxy decane, % aminopropyl propyl dialkoxy a reaction of an alkyl decane, such an anhydride or an acid dianhydride, converting an amine group of 3-aminopropyltrialkoxydecane or 3-aminopropyldialkoxyalkylnonane to an amine group A An acid ester group or a urea group or the like. Further, as the base T in this case, a methyl group, an ethyl group, a butyl group or the like may be mentioned, and as the acid liver, maleic anhydride, phthalic anhydride or the like may be mentioned, and H may be exemplified as H3. , 4,4'-benzophenonetetracarboxylic dianhydride, 4,4,-oxydi-orthocarboxylic acid dianhydride, formic acid liver, etc., as the amino-based acid vinegar group, a third butoxy group An amine group or the like is exemplified as the ureido group. The content of 3 as a binder is preferably 〇30 parts by mass relative to (a) the mass of the polyamine. I403l4.doc -20-201011469 parts. Further, as the dissolution promoter, a compound having a phenolic hydroxyl group is preferably a linear phenolated oral substance such as bisphenol, MtrisPC or MtetraPC, or a non-trisP-HAP, TrisP-PHBA or TrisP-PA. Linear phenolated σ (all manufactured by Honshu Chemical Industry Co., Ltd.); diphenylmethane, 25 phenolic substituents, 1 to 5 phenolic substituents of 3,3-diphenylpropane; 2,2_ Reaction of bis(3amino-4-pyridyl)hexafluoropropane with hexamidine-2,3-dicarboxylic anhydride φ of 1 to 2, bis(3·amino-4-hydroxyl) a reaction of phenyl) hydrazine with 1, 2 - cyclohexyl dicarboxylic anhydride of 1 to 2, and the like. The content in the case where the dissolution promoter is contained is preferably from 1 to 30 parts by mass based on the mass fraction of (a) polyamine. Examples of the crosslinking agent include tetrakis(p-hydroxyphenyl)ethane, tetraglycidyl ether, glycerol triglycidyl ether, o-t-butylphenyl glycidyl ether, and 1,6-bis ( Epoxy compounds such as 2,3-epoxypropoxy)naphthalene, diglycerin polyglycidyl ether, polyethylene glycol glycidyl ether; acetoacetate aluminum (ruthenium) salt, • titanium acetylacetonate (IV) salt, Ethyl acetonate chromium (m) salt, acetoacetone magnesium (π) salt, acetamidine acetone nickel (II) salt, trifluoroacetic acid aluminum (ruthenium) salt, trifluoroethylene acetone (IV) salt, three Metal chelating agent such as fluoroacetic acid acetone chromium (III) salt, trifluoroacetic acid magnesium (II) salt, trifluoroacetone acetone nickel (ruthenium) salt; NIKALAC MW-3 0MH, MW-100LH (trade name, three And melamine resin-based cross-linking agent such as Cymel 300 > Cymel 303 (trade name, manufactured by Mitsui-Cytec Co., Ltd.); NIKALAC BL-60 (trade name, manufactured by Sanwa Chemical Industry Co., Ltd.) ), Cymel 1123, Micoat 102, Micoat 105 (trade name, 140314.doc -21· 201011469)

Benzene cultivating cross-linking agent manufactured by Mitsui-Cytec Co., Ltd.; 1^ 〖/〇> 八(:]^:^-270, MX-280, MX-290 (trade name, manufactured by Sanwa Chemical Industry Co., Ltd.) The specific amount of the crosslinking agent is preferably 0.1 to 30 parts by mass based on the mass part of the (a) polyamidoxime. (D) Solvent

In the present invention, the components may be dissolved in a solvent to form a varnish, and used as a solution of the photosensitive resin composition. As such a solvent, it can be used singly or in combination: N-mercapto-2-pyrrolidone, γ-butyrolactone, N,N-dimercaptoacetamide, dimethyl sulfoxide, diethylene glycol dioxime ether , diethylene glycol monoethyl ether, monoethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl bond, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, lactate Ding, 1, 3 Monool methyl acetate, Μ-butanediol·3_monomethyl ether, pyruvate strontium S, thymidine, T-oxypropyl methacrylate, and the like. Among these solvents, the effect on the photoresist, etc. is small; the work_± 寻(元响比} aspect, and the non-amined solvent is preferred, as a more specific example,

J γ-butyrolactone, cyclopentanone, cyclohexanthene, isophora and so on. The content in the case where the solvent is contained in the photosensitive resin composition is relatively large; (4) The polyamine (10) parts by mass is preferably 5 Å to 1 Å by mass. <Method for Producing Hardened Relief Pattern and Semiconductor Device> For example, a method of producing a hard 4 relief pattern by applying a photosensitive resin composition onto a substrate will be specifically described. The roll coating of the roll coater, the ceramic substrate, and the aluminum base are first applied by spin coating using a spin coater or by using a photosensitive resin composition on, for example, a hard wafer, 140314.doc •22·201011469: A substrate with a resin medium is obtained. Use an oven or a hot plate to remove the solvent at 50~14 (TC). Using a contact aligner or stepper, expose the actinic ray through the reticle, or directly illuminate the light, electrons Beam or ion beam. Then 'dissolve or remove the exposed portion or the irradiated portion with a developing solution, and then, rinse the eluent to obtain the desired embossing method, which can be a spray , such as dropping, dipping, ultrasonic, etc. The eluent can be distilled water, deionized water, etc. It is used to dissolve the resin developing solution formed by the sensible resin composition to remove the polyamine, and must be The test compound dissolved in the developer may be any one of an inorganic compound and an organic basic compound. 2 For the test compound, for example, hydrogen oxygen _ , Μ, 虱 虱 虱 、, diammonium hydrogen phosphate, dipotassium hydrogen phosphate, phosphoric acid arsenal =, oligo acid clock, sodium silicate, simple, carbonic acid clock, sodium carbonate, potassium carbonate, lithium borate, sodium borate, boric acid Potassium, ammonia, etc. For example, tetramethylammonium hydroxide, tetraethyl hydride, trimethyl hydrazide, ethyl methylamine, methylamine, dimethylamine, trimethylamine, monoethylamine, Diethylamine, triethyl i:, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, methylamine, dimethylethanolamine, ethanolamine, triethanolamine, etc. It is necessary to add an appropriate amount of methanol, ethanol propanol, ethylene glycol, etc., such as water-soluble right mother, depleted W stabilizer, resin dissolution inhibitor, etc., surfactant, and storage in the above-mentioned aqueous solution. 140314.doc - 23- 201011469 Finally, the obtained relief pattern is heat-treated to form a hardened relief pattern having a polybenzoxazole structure and/or a polyimide structure. As a heating device for performing heat treatment, It can be used as a heating method, such as a hot box furnace, a heating plate, a vertical furnace, a conveyor belt furnace, a pressure oven, etc., and it is recommended to use hot air, infrared, electromagnetic induction heating. The temperature is preferably 200 to 450 ° C, better. It is 250 to 400 ° C. The heating time is preferably 15 minutes. 8 hours, more preferably 1 hour to 4 hours. The ambient gas is preferably in an inert gas such as nitrogen or argon. The semiconductor device can be rewired by using a hardened relief pattern as a surface protective film and an interlayer insulating film. A protective film made of an insulating film, a protective film for a flip chip device, or a device having a bump structure is produced in combination with a known method of mounting a semiconductor device. The hardened relief pattern produced by the above manufacturing method is not only It is used for semiconductor applications, and is also used as an interlayer insulating film of a multilayer circuit or a protective layer of a flexible copper box, a solder resist film, a liquid crystal alignment film, etc. [Embodiment] The present invention is based on Reference Examples, Examples, and Comparative Examples. More specifically, &lt;Synthesis of Polyamide&gt; [Reference Example 1] In room temperature (25) in a separable flask having a capacity of 2 liters. 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 197.8 g (〇.54 mol), 71.2 g (〇.9 mol), N,N-dimethyl Ethylamine (hereinafter also referred to as "DMAc") 692 g was mixed and stirred to dissolve the diamine. Among them, 140314.doc • 24· 4 201011469 29.6 g (0.18 mol) of 5-norfos-2,3-dicarboxylic acid needle was dissolved in diethylene glycol dimethyl ether by dropping from a dropping funnel (hereinafter, Also known as DMDGj) 88 g. The time required for the dropwise addition was 4 minutes, and the temperature of the reaction liquid was at most 28 °C. After the end of the business, warm up to 50 by hot water bath. After stirring for 18 hours, the IR spectrum of the reaction mixture (infrared spectr〇sc〇py, infrared spectrum) was measured, and it was confirmed that the characteristic absorption of the imino group of 1385 em·1 and 1772 cm·1 was exhibited.

Then, it was cooled to 8 by a water bath. In the above, a solution of 4,4·-diphenyl ether dimethyl hydrazine 13 8 g (〇 45 m〇1) was dissolved in DMDG 398 g from the dropping funnel. The time required for the addition is 8 minutes and the reaction temperature is at most 12. (: After the completion of the dropwise addition to 3 hours, the above reaction liquid was added to 12 L of water under high-speed stirring to disperse the polymer, and the polymer was recovered, washed with water, dehydrated, and vacuum dried. The polyamine (p-1) was obtained. The weight average molecular weight measured by Gpc of the polyamine (P-i) synthesized in the above manner was 8,9 Å in terms of polystyrene. [Reference Example 2] In a separable flask having a capacity of 2 liters, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane 293 〇g (〇8 〇 〇 1) was mixed under a dry nitrogen stream. 253.1 g (3.2 mol) of pyridine is dissolved in 2.0 liters of acetone, and cooled to _15. 〇. 35 benzenetricarboxylic anhydride hydrazine dissolved in acetone 500 (6) is added dropwise thereto in such a manner that the temperature of the reaction liquid does not exceed 吖370.6 g (176 (4)). Adding the knot 140314.doc -25- 201011469 After the bundle, react at 〇 ° C for 4 hours. Concentrate the solution with an evaporator and then put it into 5 liters of petroleum hydrazine to obtain acid Sf ( 6FA). In a separable flask of 3 liters, the anhydride (6FA) was mixed with 357.2 g (0.5 mol) and 3-hydroxybenzyl alcohol 136.6 g ( Ii m〇l), NMP 1.25 liters, "bite 87. 0 g (ll mol), then mix at room temperature! 6 hours for esterification. Then add '1-hydroxy·1,2,3 - Benzene three bites 148.64 g (ll mol) 'added under ice cooling to dicyclohexylcarbodiimide (DCC) 227.0 g (ll mol) dissolved in NMP 230 g a dicarboxylic acid derivative. Then, a solution of 4,4'-diaminodiphenylphosphonium.ig (0.55 mol) dissolved in NMP 0.35 liter was added to the reaction mixture, and the reaction was stirred at room temperature. 3 hours. Thereafter, 32.8 g (〇. 2 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added, and further reacted at room temperature for 4 hours. The reaction solution was filtered to remove insoluble components, and then poured into In a solution of water/sterol = 10/1, the precipitate was collected by filtration and dried under reduced pressure to obtain a polydecylamine (P-2) having a Gpc molecular weight of 9,400 (in terms of polystyrene). Synthesis of a nitrogen hydrazine compound &gt; [Reference Example 3] In a separable burn-in plate to which 1 liter of a stirrer, a dropping funnel, and a thermometer are attached, 'the structural formula is used as a poly-based compound: 140314.doc 201011469 [化22]

-OH CHj Compound (manufactured by Asahi Organic Materials Co., Ltd., trade name: mMC_BZ) 15.0 g (0.05 mol) '1,2-naphthoquinone equivalent to 9% of its 〇H group One azide-4-sulfonium gas 24.2 g (〇.09 m〇l) was stirred and dissolved in acetone • After 197.4 g, the flask was adjusted to 3 (TC in a constant temperature bath), at a fixed speed for 30 minutes. The solution was diluted with 47 8 g of acetone to triethylamine 9 % g. At this time, the reaction liquid was controlled in an ice water bath to control the temperature in the range of 20 to 30 C. After the completion of the dropwise addition, further 2 〇 After stirring for 3 minutes, the mixture was poured into 36 g of a 36% by mass aqueous hydrochloric acid solution, and then the reaction liquid was cooled in an ice water bath, and the precipitated solid matter was subjected to suction filtration. The filtrate was added dropwise to 5 liters of a hydrochloric acid aqueous solution having a concentration of 0.5% by mass for 1 hour, and the target product was precipitated, and subjected to suction filtration to be recovered. The obtained cake-like recovered product was again dispersed in ion-exchanged water. 3 liters, stir, wash, filter and recycle, and repeat 3 times of this washing operation. Finally, The obtained filter cake was vacuum-dried at 40 ° C for 48 hours to obtain a photosensitive diazonaphthoquinone compound [Reference Example 4] except that 1,2-naphthoquinonediazide was used in Reference Example 3 4-According to the fact that the helium gas becomes 25.5 g (0.095 mol), the same operation is carried out to obtain the photosensitive diazonaphthoquinone compound (Q-2). 140314.doc -27- 201011469 [Reference Example 5] Except for the reference example 3, except that 1,2-naphthoquinonediazide-4-sulfonyl chloride was changed to 丨'2 naphthoquinonediazide-5-sulfonyl chloride 24_2 g (0.09 mol), and the same operation was carried out to obtain photosensitivity. The diazonaphthoquinone compound (Q·3). [Reference Example 6] In a separable flask equipped with a stirrer, a dropping funnel, and a thermometer, the following formula was used as a polyhydroxy compound. twenty three]

The compound represented by the company (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Dingshi 1&gt;-PA) 30 g (0.0707 mol) '1,2-naphthalene equivalent to 76 7 m〇i% of its 〇H group After the hydrazine diazide_4_sulfonate gas 43.69 g (〇.163 m〇i) was stirred and dissolved in 300 g of acetone, the flask was adjusted to 3 Torr in a thermostat. Then, triethylamine 2L0 g was dissolved in 18 g of acetone, placed in a dropping funnel, and then added dropwise to the flask t in 3 minutes. After the completion of the dropwise addition, the continuous dropping was carried out for 3 minutes, and then the dropwise addition of hydrochloric acid was carried out to carry out the reaction of the cycle clock, and the reaction was carried out, and the triethylamine hydrochloride was removed by filtration. While stirring, the precipitate obtained here was added to a beaker which was mixed with pure water and purchased in a 3 liter beaker of pure water of 140314.doc -28-201011469 g and 30 g of hydrochloric acid to obtain a precipitate. The precipitate was washed with water and filtered, and then dried at 40 ° C for 48 hours under reduced pressure to obtain a photosensitive diazonaphthoquinone compound (Q-4). [Reference Example 7] A photosensitive diazonaphthoquinone compound was obtained by performing the same operation except that the 1,2-naphthalene diazide-4-sulfonium gas was changed to 53.19 g (0.198 mol) in Reference Example 6. (Q-5). [Reference Example 8] Except that in the Reference Example 6, 1,2-naphthoquinonediazide_4_sulfonium gas was changed to 12_naphthoquinonediazide-5-continued helium gas of 43.69 g (0.163 mol), The same operation was carried out to obtain a photosensitive diazonaphthoquinone compound (Q-6). [Reference Example 9] In a 1 liter separable flask equipped with a stirrer, a dropping funnel, and a thermometer, the following structural formula was used as a polyhydroxy compound: [Chem. 24]

The compound represented by the company (manufactured by Honshu Chemical Industry Co., Ltd., trade name: Bisp_AP) 29.36 g (0.100 mol), which is equivalent to 9〇m〇1% of its 〇H group, 1,2-naphthoquinone azide After -4-sulfonyl chloride 48.36 g (〇.180 m〇i) was stirred and dissolved in 300 g of acetone, the flask was adjusted to 3 Torr in a constant temperature bath. Then, 19.1 g of triethylamine was dissolved in 18 g of acetone, placed in a dropping funnel, and added dropwise to the flask at 140314.doc -29-201011469 for 30 minutes. After the completion of the dropwise addition, the mixture was further stirred for 3 minutes, and then hydrochloric acid was added dropwise thereto, and the mixture was further stirred for 30 minutes to complete the reaction. Then, filtration was carried out to remove triethylamine hydrochloride. The precipitate obtained here was added to a beaker which was mixed and stirred with a pure water 丨 64 〇 g and 30 g of hydrochloric acid in a 3 liter agitator to obtain a precipitate. The precipitate was washed with water and filtered, and then dried at 40. (:, drying under reduced pressure for 48 hours to obtain a photosensitive diazonaphthoquinone compound (Q-7). [Reference Example 10] In a 1 liter separable flask equipped with a stirrer, a dropping funnel, and a thermometer' The following structural formula is used as a polybasic compound: [Chem. 25]

The compound represented (manufactured by Honshu Chemical Industry Co., Ltd., trade name: ph_CC-AP) 15.32 g (0.050 mol) '1,2-naphthoquinonediazide-4 which is equivalent to 90 mol% of its oh group - 36.27 g (0.135 mol) of sulfonium gas was dissolved in 300 g of acetone, and the flask was adjusted to 3 (rc ^ in a thermostat, then 14.3 g of diethylamine was dissolved in 8 g of acetone oxime, and dropped into a drop. After the liquid funnel, the mixture was added dropwise to the flask over 30 minutes. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes, and then hydrochloric acid was added dropwise thereto, and the mixture was stirred for 3 minutes to complete the reaction. Then, filtration was carried out. The triethylamine hydrochloride was removed, and the filtrate obtained here was added to a beaker which was mixed with pure water 164〇140314.doc -30-201011469 g and 30 g of hydrochloric acid in a 3 liter beaker. The precipitate was washed with water and filtered, and then dried at 40 ° C for 48 hours under reduced pressure to obtain a photosensitive diazonaphthoquinone compound (Q-8). &lt;Preparation of photosensitive resin composition and Evaluation> [Examples 1 to 4 and Comparative Examples 1 to 5]

According to the combination of the following Table 1, 100 parts by mass of the polydecylamine (P-1, 2) obtained in each of the above Reference Examples, and 2 parts by mass of the diazonium compound (q_i to 8) were dissolved in 200 parts by mass of GBL. After that, the photosensitive resin composition was prepared by filtration using a filter of 〇.2 μηη, and the patterning property and the varnish precipitation stability were evaluated. (1) Evaluation of Patterning Characteristics The above-mentioned photosensitive resin composition was spin-coated on a 6-inch 夕石βββ circle by a spin coater (Clean Track Mark-8) manufactured by Tokyo Electron Co., Ltd. Heat the plate at 12 inches. The undercoat was pre-baked for 18 sec seconds to form a 11.7 μηι coating film. The film thickness was measured by a film thickness measuring device (Lambda Ace) manufactured by Dainipp0n screen MFG. For the coating film, a stepping machine (NSR2〇〇5i8A) manufactured by Nikon Co., Ltd. having an exposure wavelength of 丨 (365 nm) was used, and the exposure amount was changed stepwise by a photomask attached with a test pattern. Exposure. Using an alkaline developer (AZ300MIF developer, 2.38% by weight aqueous solution of tetramethylammonium hydroxide) manufactured by AZ Electronic Materials, at 23 ° C, the development was adjusted to develop the image to develop The film thickness became 9.4 tons' to form a positive pattern. The sensitivity and resolution of the photosensitive resin group a are shown in Table 1 below. 140314.doc -31 - 201011469 Further, the sensitivity and resolution of the photosensitive resin composition were evaluated in the following manner. [Sensitivity (mj/cm2)] In the above development time, the minimum exposure amount of the exposed portion of the coating film can be completely dissolved. [Resolution (μηι)] The minimum resolution pattern size under the above exposure amount. (2) Evaluation of precipitation stability The prepared photosensitive resin composition was filtered, and after standing at room temperature and -20 C for a week, it was visually observed whether or not solid matter was observed in the varnish. In Table 1, when no precipitation is observed, it is represented by "〇", and when it is seen, it is represented by "X". [Table 1] Table 1

According to Table 1, it can be seen that by using the photosensitive resin composition of the present invention, a pattern having high sensitivity and high resolution can be formed with an appropriate development time, and 'no precipitation is formed. On the other hand, the compositions of Comparative Examples 1 to 5 which did not contain the diazonium compound satisfying the requirements of the present invention were inferior in sensitivity and resolution, and the composition of Comparative Example 2 was precipitated in 1403l4.doc 201011469. [Industrial Applicability] The photosensitive resin composition of the present invention can be preferably used for forming a surface protective film such as a semiconductor element, an interlayer insulating film, or the like.

140314.doc -33-

Claims (1)

201011469 VII. Application for a patent garden: 1. A photosensitive resin composition comprising: (4) a polystyrene having a structure represented by the following formula (1): (10 parts by mass): '[Chemical 1] jOH)p ( 〇H)q -HN -Xl-NHC0_ 十丨~c〇___ (1) _ (COOR)m {wherein, Xl is a 2~4 valence organic group having 2 or more carbon atoms, and A is 2 or more 2 to 6 valence organic groups of carbon atoms, ... are each independently an integer of 〇~4' R is a hydrogen atom or an organic group having a carbon number of 丨~2〇, an integer of 0 to 2, an integer of _~_, Wherein, melon, p and ^ are not 0 at the same time, and when both 15 and 〇1 are 〇, R is a group having a phenolic hydroxyl group; and (b) is represented by the following formula (2) Nitrogen bismuth compound diterpenoid (9) parts by mass: [Chemical 2] In the formula, A, Z2 and &amp; independently are carbon numbers for the "i-valent organic groups' a and b are each an integer of 〇~4, (; is an integer of 〇~5, a plurality of Qs Any one is as follows: 140314.doc 201011469 [化3] 2 The two bases represented The compound is a compound represented by the following formula (3). In the formula, any one of the plurality of Qs is as follows [Chemical 5] Any one of the two bases indicated is 'the rest is a hydrogen atom}. 3. The request item is a photosensitive resin composition, wherein the above (4) polyamin has a repeating unit represented by the following formula (4): 140314.doc (4) 201011469 [Chem. 6] _ book~ sub 2 - NHCO —Y2—CO· 〇H η {wherein Χ2 is a tetravalent aromatic group' 丫2 is a divalent aromatic group, and an integer of 2 to 1000 is 4. A method for producing a hardened relief pattern, which includes The following steps: a step of applying a photosensitive resin composition according to any one of items 1 to 3 to a substrate; 'exposing or directly irradiating light, an electron beam or an ion beam with actinic rays through a photomask a step of eluting or removing the exposed portion or the irradiated portion; and a step of heating the obtained relief pattern. A semiconductor device having a hardened relief pattern obtained by the method of claim 4. 140314.doc 201011469 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 of the characteristics of the invention. Chemical formula: (none) 140314.doc -2-