TW201033251A - Positive type photosensitive polyimide resin composition - Google Patents

Abstract

Provides is positive type photosensitive polyimide resin composition which is able to proceed with processing of fine pattern, close to heat resistance of coat and coefficient of linear expansion of substrate and alkaline developable without imidization at high temperature. Positive type photosensitive polyimide resin composition contains polyimide resin having ester bonding on main chain, having specific skeleton with phenolic hydroxyl group on at least one of main chain and side chain and solubilizing in organic solvent, and compound which generates acid by active ray irradiation.

Description

[Technical Field] The present invention relates to a positive-type photosensitive polyimide resin composition, which is used as an electrical or electronic insulating material for improving the reliability of a semiconductor device, and the like. Semiconductor surface insulation film user. [Prior Art] Conventionally, a polyimide resin having excellent heat resistance, electrical properties, properties, and the like is used for the surface protective film and the interlayer insulating layer of a semiconductor element. However, in recent years, in the progress of semiconductor element formation and large-scale development, there has been a demand for a thinner sealing resin package, and a pin is connected across a wafer (LOC: lead 〇 lead-free reflow soldering surface adhesion, etc. In order to achieve weight reduction, high integration, and high density, the circuit board or the half part used in an electronic device has been used in recent years in addition to a polyimide resin having excellent mechanical properties and heat resistance. Ultra-fine refinement has progressed rapidly. In this process, the difference in linear expansion coefficient between the board and the member material has not been greatly affected by the product quality. The dimensional stability that solves the problem is strongly different. On the one hand, the polyimide resin itself is used to impart photosensitive photopolymerization, and when used, it has the characteristics of simplifying the drawing step and shortening complicated manufacturing steps. Negative medium method: Polyimine precursor (proline) is based on ester bonds, ionic bonds, in the manufacture, high or small layers of protective or mechanical films, protective and mechanical components, or In addition, it is a method of introducing a methacrylic fluorenyl group by the following, a guanamine bond 201033251 or an IPN type, etc. 5) a soluble polyimine having a photopolymerizable olefin (for example, refer to Patent Document 6); a debenzoate having a benzophenone skeleton and having an alkyl group in the ortho position of the nitrogen ring-bonded aromatic ring The sensitizing type polyimine (see, for example, Patent Documents 7 and 8); a soluble polyimine having a furan structure (for example, see Patent Document 9) by photo-oxidation-excitation polymerization. However, in these negative types, since an organic solvent such as N-methylpyrrolidone which is unfavorable to the environment is used in the development step, there is a problem in safety in the development step, and in recent years, a development has been replaced. The negative type is a positive photosensitive polyimide resin which is developed with an aqueous alkali solution. The positive-type heat-resistant resin composition in which the exposed portion is developed and dissolved is one in which polyheptamic acid is added with naphthoquinone diazide (for example, refer to Patent Document 10); and a poly-proline which has a hydroxyl group is added Naphthoquinone diazide (for example, refer to Patent Document 11); a photoacid generator (PAG)/photobase generator (PBG) is added to a polyamidene precursor having an acid/base decomposition group (for example, reference) Patent Documents 12 and 13); a fluorene-nitrobenzyl group is introduced into a polyimide precursor (for example, see Patent Document ❹ 14). In the case of using a polyimine precursor, either of the above methods, after photoprocessing, it is necessary to carry out a heat-treated ruthenium ring closure, in which case, with the dehydration of the ruthenium ring and the cross-linking component Volatilization shrinks the volume, and the disadvantage of causing loss of film thickness and reduction in dimensional stability cannot be avoided. In addition, the heat treatment step in the high temperature of the ring closure reaction may cause deterioration of other electronic parts or organic materials. Although a sensitizer of a polyimine which is inherently soluble in an organic solvent which does not require a cyclization process is proposed (positive type, for example, Ref. 201033251, Patent Documents 15 to 18), these are photosensitive, heat-resistant, and mechanical. And the disadvantage of any inferiority in dimensional stability. Therefore, in fact, none of them has reached the level of practical use. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. JP-A No. Hei 59-108031 [Patent Document 7] JP-A-61-145794 (Patent Document No. JP-A-61-145794) [Patent Document 10] JP-A-2000-338668 (Patent Document 10) JP-A-52-0 1 3 3 1 5 [Patent Document 11] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 60-037550 (Patent Document No.). Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 249454 SUMMARY OF INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a positive photosensitive property. The quinone imine resin composition 201033251, which can reduce the problem of the prior art such as a decrease in the adhesion to the substrate or the warpage of the substrate due to the large thermal expansion coefficient of the conventional positive photosensitive resin. At the same time, it solves the problem that the surface of the semiconductor device or the like is greatly affected by the formation of the surface protective film or the interlayer insulating film by the high temperature heated by the hydrazine imidization and the water generated by the hydrazine imidization reaction. And reducing the coefficient of thermal expansion, thereby reducing the adhesion to the substrate or reducing the warpage of the substrate; and not because of the high temperature of the heating in the imidization of the hydrazine and the water produced by the imidization reaction. In the case of forming a surface protective film or an interlayer insulating film, it is greatly affected by a product such as a semiconductor device, and a heat resistant resin film which does not deteriorate electrical properties, resolution, or the like can be imparted. Further, the present invention provides a pattern production method which is capable of obtaining a pattern of a good shape which is excellent in heat resistance, mechanical properties, and thermal dimensional stability after alkali development and low-temperature heat treatment by use of the above composition. Further, the present invention provides a highly reliable electronic component via a pattern having a good shape and characteristics. [Means for Solving the Problem] The present inventors have reached the following invention by focusing on the results of continuous research in view of the above circumstances. The present invention is characterized in that it has an ester bond in a main chain, and at least one of a main chain and a side chain has a phenolic hydroxyl group-containing polyimine and a photoacid generator as an essential component, thereby achieving The above purpose. That is, the present invention is a constituent of the following. A positive photosensitive polyimide resin composition characterized by comprising (a) a tetracarboxylic dianhydride having an ester bond in a molecule represented by the following formula (Chemical Formula 1), and a formula of 201033251 a polydiimide resin obtained by reacting an aromatic diamine represented by (Chemical Formula 2) and/or an aromatic diamine represented by the formula (Chemical Formula 3) (and also including the salt thereof), and activated light a compound that produces acid when irradiated; [Chemical 1]

(wherein X represents a divalent group containing an aromatic ring) [Chemical 2]

(wherein represents hydrogen, a carboxylic acid group, an alkyl group, a fluorine-substituted alkyl group, an alkoxy group or a halogen group; η represents an integer from 〇 to 4' wherein '11 R! are the same or different substituents ;m represents an integer greater than 1) [Chemical 3]

201033251 (wherein A is selected from any of a group consisting of a group represented by -C(=0)0-, -NHCO-; at least one of R2, R3 and R4 is a hydroxyl group; Other means that the carboxylic acid group, the alkyl group, the fluorine-substituted alkyl group, the alkoxy group or the halogen group 'is the same or different groups; p, q, r and s represent an integer of 0 to 4, P + q + r^l, (s+l) A can be the same or different). • A positive photosensitive polyimide resin composition as described in the above, wherein the polyimine resin contains a repeating unit represented by (Chemical Formula 4), [Chemical 4]

(wherein, X represents a divalent group containing an aromatic ring; and W is derived from a structural unit of a diamine represented by the formula (Chemical Formula 2) or the general formula (Chemical Formula 3)). The positive-type photosensitive polyimide resin composition according to any one of the above-mentioned items, wherein the structure of the formula (Chemical Formula 3) is a diamine represented by the following formula (Chemical Formula 5). 5]

(wherein A is selected from any of a group consisting of a group represented by -C(=0)0-, -NHCO-; Rs, R6 represents an alkyl group, a fluorine-substituted alkane a group, an alkoxy group or a halogen group, which are the same or different groups; X, y represents an integer of 0 201033251 to 4, x + ygl). The positive-type photosensitive polyimide resin composition as described in any one of the above-mentioned, wherein the structure of the formula (Chemical Formula 3) is a diamine represented by the following formula (Chemical Formula 6), [Chemical 6]

(wherein A is selected from any of a group consisting of a group represented by -C(=0)0-, -NHCO-; and R5, R6 represents an alkyl group, a fluorine-substituted alkane. a group, an alkoxy group or a halogen group, which are the same or different groups; x, y represents an integer from 0 to 4, x + ygl). The positive photosensitive polyimide resin composition according to any one of the preceding claims, wherein the compound which generates an acid upon irradiation with an activating light is an esterified quinonediazide compound.醯 醯 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种 一种After development of alkaline water such as an aqueous solution of ammonium methoxide, heat treatment is carried out at a temperature of 25 Torr or less. [Effect of the Invention] According to the present invention, since a polyimide having a specific structure is used, a high elastic modulus, an excellent thermal dimensional stability, and a solvent solubility balance can be satisfactorily achieved. The polyimine which is derived from the positive photosensitive polyimide resin composition of the present invention has a small thermal expansion coefficient and can be formed only by coating and drying on a substrate having a low thermal expansion of 201033251, such as a tantalum wafer. A resin film such as an insulating film does not require a ruthenium imidization process to make the difference in thermal expansion coefficient small, and the adhesion to the substrate is good, and warpage can be reduced. Further, since the development property and the photosensitivity can be favorably maintained, a good pattern can be obtained from these results, and it is extremely effective as an electrical and electronic insulating material in the production of a semiconductor device or the like. [Embodiment] Hereinafter, embodiments of the present invention will be described, and these are merely examples of the embodiments of the present invention, and are not limited by the contents. The soluble polyimine in the present invention is soluble in an organic solvent (solvent). If it is insoluble in an organic solvent, it is necessary to form a polyimine layer by using a polyimine precursor and undergoing a dehydration ring closure reaction. At the time, since a high-temperature process of 350 ° C or higher is required, it is feared that thermal deterioration of the semiconductor device is caused. In addition, the term "organic solvent" is used herein to mean that at least 1% by mass or more of the polyimine is dissolved in at least one organic solvent selected from the group consisting of the following organic solvents. Examples of the organic solvent include those having a boiling point of not more than 550 °C. The preferred example is a boiling point of 300 rpm or less. More preferably, the boiling point is 260 ° C or less. Specific examples thereof include an anthraquinone solvent such as p-chlorophenol or m-cresol; N-methyl-2-pyrrolidone, N,N-dimethylformamide, and N,N-dimethyl group. A guanamine-based solvent such as guanamine; or γ-butyrolactone, γ-valerolactone, δ-valerol, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc. A cyclic ester solvent or the like. <Maintenance of this embodiment> As described in the present embodiment, a polyimine polymer can be provided, which is represented by the general formula (Chemical Formula 1). ) an acid dianhydride as shown, which is obtained by polymerizing a diamine represented by the formula (diamine or the formula (Chemical Formula 3); [Chemical Formula 1]

(wherein X represents a divalent group of an aromatic ring). [Chemical 2]

Wherein 'R! represents hydrogen, a carboxylic acid group, an alkyl group, a fluorine-substituted alkyl group or a halogen group; η represents an integer of 0 to 4, wherein η Ri or a different substituent; m袠An aromatic amine represented by an integer of 1 or more, and/or a general formula (Chemical Formula 3). , the courtyard oxygen is the same, the fragrance two [Chemical 3]

-11- 201033251 (wherein A is selected from any of a group consisting of a group represented by _C(=0)0_, -NHC.O-; at least R2, R3, and R4 One is a hydroxyl group, the other represents a carboxylic acid group, an alkyl group, a fluorine-substituted alkyl group, an alkoxy group or a halogen group, which are the same or different groups; p, q, r and s represent an integer of 0 to 4 , P + q + r21, (s + l) A can be the same or different). In the above polyimine, the diamine represented by the formula (3) is preferably a diamine represented by the formula (5). [Chemical 5]

❹ (wherein A is selected from any of a group consisting of a group represented by -C(=0)0-, -NHCO-; Rs, Re represents an alkyl group, and is substituted by fluorine. An alkyl, alkoxy or halogen group, which is the same or a different base; X, y represents an integer from 〇 to 4, χ + y 2 1). Further, in the above-mentioned soluble polyimine polymer, the diamine represented by the formula (3) is preferably a diamine represented by the formula (6). [Chemical 6]

-12- 201033251 (wherein A is selected from any of a group consisting of a group represented by -C(= 〇)〇-, -NHCO-; R5, 116 represents an alkyl group, A fluorine-substituted alkyl, alkoxy or halogen group is the same or a different group; X, y represents an integer from 0 to 4, x + yg 1 ). Alternatively, a polyimine polymer containing a repeating unit represented by the formula (Chemical Formula 4) can be provided as in the present embodiment. [Chemical 4]

(wherein, X represents a divalent group containing an aromatic ring; and W is derived from a structural unit of a diamine represented by the formula (2) or the formula (3)). Further, in the lacquer formed of the organic solution containing the above polyimine, the photosensitive resin composition obtained by dissolving a compound which generates an acid by irradiation with an active light and forming a film by casting has excellent photosensitive characteristics. . Then, the fine pattern of the film containing the polyimide pigment polymer can be suitably obtained according to the following production method, and the following production method includes: coating the above-mentioned positive type photosensitive resin composition to form a positive photosensitive resin composition a step of forming a film, a step of patternwise exposing the film of the positive photosensitive resin composition, a step of performing alkali development on the film of the positive photosensitive resin composition subjected to pattern exposure, and a step of forming an alkali-developed positive photosensitive resin The step of heat-treating to form a polyimide film. That is, as in the present embodiment, as described above, a poly(ester) quinone imine polymer film having a high permeability of 13-201033251 can be realized, and a poly(ester) quinone imine polymer film can be realized. A positive-type photosensitive resin composition containing a sensitizer, and an optimum polyester phthalimide polymer film obtained as an electronic product (part) obtained by an alkali development, cleaning, and hardening step after exposure thereto A method of manufacturing a fine pattern. <Method for Producing Polyimine Polymer of the Present Embodiment> The method for producing the polyimine polymer is not particularly limited, and a suitable conventional method can be used. More specifically, it can be obtained by the following method. First, one or more kinds of diamines (including salts thereof) represented by the above formula (Chemical Formula 2) or Formula (Chemical Formula 3) are dissolved in a dehydrated polymerization solvent, and the formula (Chemical Formula 1) is added thereto. The acid dianhydride was stirred under a nitrogen atmosphere. In all of the tetracarboxylic dianhydrides used for the polymerization, the content of the rigid tetracarboxylic dianhydride represented by the formula (Chemical Formula 1) is preferably in the range of 50 mol% or more, more preferably 75 mol% or more, and less than 50%. In the case of mol%, it is feared that the required characteristics such as the coefficient of thermal expansion and the modulus of elasticity are significantly lowered. In the range of the non-destructive and polymerizable reactivity and the desired properties of the polyimine, the poly(ester) quinone imine is represented by the formula (Chemical Formula 1) in the polymerization. The tetracarboxylic dianhydride which can be used, other than the tetracarboxylic dianhydride, is not particularly limited, but has an aromatic ring group or aromatic hetero group having a carbon number of 6 to 30 in order to impart heat resistance to the polyiminimide. The base of the ring base is preferred. Examples of preferred aromatic tetracarboxylic anhydrides include, for example, pyromellitic anhydride, biphenyl-3,4,3,4·-tetracarboxylic dianhydride, benzophenone-3, 4, 3, 4 ·-tetracarboxylic dianhydride, oxydiphthalic acid dianhydride, diphenyl hydrazine-3,4,3',4'-tetracarboxylic dianhydride, 4,4·-(2,2-hexafluoroisopropylene Dialkyl phthalic anhydride, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-14- 201033251

-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2, 4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3-(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3·(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethyl Cyclohex-1-ene-3-(1,2),5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1-(1,2), 3,4-tetracarboxylic dianhydride , 1-propylcyclohexane-1-(2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3), 3-(2 , 3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid Dihydride, 1-propylcyclohexane-l-(2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3),3- (2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetra Carboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylate Acid dianhydride, etc., in order to maintain the low coefficient of linear expansion, use the pyromellitic anhydride structure or the following formula (Chemical 7) to An acid anhydride of a biphenyl-3,4,3',4'-tetracarboxylic dianhydride structure represented by (Chemical Formula 8) is preferred. These tetracarboxylic dianhydrides may be used singly or in combination of two or more. [Chemistry 7]

(wherein R7 represents a phenyl group, a 3-biphenyl group, a 4-biphenyl group, a 1-naphthyl group or a 2-naphthyl group) 15-201033251 [Chem. 8]

(wherein R8 represents a phenyl group, a 3-biphenyl group, a 4-biphenyl group, a 1-naphthyl group or a 2-naphthyl group). In the range of the non-destructive and polymerization reactivity and the desired properties of the polyimine, the poly(imine) in the polymerization is 'general (chemical) 2 or generalized) 3) The aromatic diamine which can be used other than the diamine shown is not particularly limited, and examples thereof include 4,4'-bis(3-aminophenoxy)biphenyl and bis[4- (3-Aminophenoxy)phenyl]one, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy)phenyl]anthracene , 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1, 3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminodiphenyl Ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3, diaminodiphenyl sulfide, 3,3'-diaminodi Phenyl anthracene, 3,4'-diaminodiphenylarsin, 4,4'-diaminodiphenylarylene, 3,3, diaminodiphenyl maple, 3,4, 2 Aminodiphenyl hydrazine, 4,4'-diaminodiphenyl maple, 3,3'-diaminobenzophenone, 3,4 --Diaminobenzophenone, 4,4, diaminobenzophenone, 3,3'-diaminodiphenylmethane. -16- 201033251 3,4·-Diaminodiphenylmethane, 4,4i-diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl]methane, 丨, 丨- bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, hydrazine, hydrazine-double μ- (4-Aminophenoxy)phenyl]propane, 1,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminobenzene) Oxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propyl, 1,1-bis[4-(4-aminophenoxy)phenyl Dingyuan, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, 1,4-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-Obis[4-(4-aminophenoxy)phenyl]butane. 2-[4-(4-Aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3-methylphenyl]propane, 2,2-bis[4- (4•Aminophenoxy)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy) ) 3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4] -(4-Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,3- Bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, double® [4 -(4-Aminophenoxy)phenyl]one, bis[4-(4-aminophenoxy)phenyl] sulfide, bis[4·(4.aminophenoxy)phenyl] Athene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy) Phenyl]ether, 1,3-bis[4-(4-aminophenoxy)benzylidene]benzene, 1,3-bis[4-(3-aminophenoxy)benzene Mercapto] benzene, 1,4-bis[4-(3-aminophenoxy)benzylidene]benzene, 4,4·-bis[(3-aminophenoxy)benzylidene] Benzene, hydrazine, 1·double [4-(3- Phenoxy)phenyl]propane, 1,3-bis[4-(3-aminophenoxy)phenyl]propane, 3,4,-diaminodiphenyl sulfide, 2,2- Bis[3-(3-aminophenyl-17-201033251 oxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis[4-(3-aminophenoxy) Phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane , bis[4-(3-aminophenoxy)phenyl] yafeng, 4,^-bis[3-(4-aminophenoxy)benzylidene]diphenyl ether, 4,4 '-Bis[3-(3-Aminophenoxy)benzylidene]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl) Phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylhydrazine, bis[4-{4 -(4-Aminophenoxy)phenoxy}phenyl]indole. 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4_(4-aminophenoxy) Phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α, α-dimethylbenzene Methyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)-α, α-dimethylbenzyl]benzene, 1,3-bis[4-(4 -amino-6-methyloxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-cyanophenoxy)-α, α-Dimethylbenzyl]benzene, 3,3·-diamino-4,4·-diphenoxybenzophenone, 4,4′-diamino-5,5′-_ Phenoxybenzophenone, 3,4'-diamino-4,51-diphenoxybenzophenone,

Q 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino-4- Phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-di-biphenyloxydiphenyl Methyl ketone, 4,4'-diamino-5,5'-di-biphenoxybenzophenone, 3,4|-diamino-4,5'-di-biphenyloxydiphenyl Methyl ketone, 3,3l-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamine -4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis(3-amino-4-phenoxybenzene) Mercapto) benzene, 1,4-bis(3-amino-4-phenoxybenzene-18-201033251 fluorenyl)benzene, 1,3-bis(4-amino-5-phenoxybenzene) Mercapto) benzene, i, 4_bis(4-amino-5-phenoxybenzylidene)benzene, 1,3·bis(3-amino-4_biphenoxy benzhydryl Benzene, 1,4-bis(3-amino-4-biphenoxybenzhydryl)benzene, 1>3_bis(4-amino-5-biphenoxybenzylidene)benzene, 1,4-bis(4-amino-5-biphenoxybenzhydryl)benzene, 2,6-bis[4-(4-amino-α, α- Methylbenzyl)phenoxy]benzonitrile and some or all of the hydrogen atoms of the aromatic ring in the above aromatic diamine via a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, cyanide a halogenated alkyl group or alkoxy-substituted aromatic diamine having a hydrogen atom of a part or all of an alkyl group or an alkoxy group substituted by a halogen atom, in order to maintain a low coefficient of linear expansion It is preferred to use p-phenylenediamine. These diamines may be used alone or in combination of two or more. In the range of the non-destructive and polymerization reactivity and the desired properties of the polyimine, the poly(imine) of the present embodiment has a general formula (Chemical Formula 2) or a general formula. The aliphatic diamine which can be used in parts other than the diamine shown is not particularly limited, and examples thereof include 4,4'·methylenebis(cyclohexylamine), @isophoronediamine. , trans-1,4·diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-cyclohexanedimethylamine, 2,5-bis(aminomethyl)di Ring [2,2,1]heptane, 2,6-bis(aminomethyl)bicyclo[2,2,1]heptane, 3,8-bis(aminomethyl)tricyclo[5, 2,1,〇]decane, 1,3-diamine adamantane, 2,2-bis(4-aminocyclohexane)propane, 2,2-bis(4-aminocyclohexane)6 Fluoropropane, 1,3-propanediamine, iota, 4_tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, anthracene, 7-heptylenediamine, 1,8-octa Methylenediamine, 1,9-non-methylenediamine, and the like. These may also be used in more than two types. The monomer mixing ratio (mole-19-201033251 ratio) when synthesizing the polyimine resin of the present invention is expressed by the method of tetracarboxylic acid (anhydride)/diamine, which is 0.800 to 1.20 0/1.200 to 0.800. It is better to use 0.900 to 1.100/1.100 to 0.900, and preferably 0.950 to 1.15 0/1.150 to 0.950. In order to block the molecular terminal of the present invention, a terminal blocking agent such as a dicarboxylic anhydride, a tricarboxylic anhydride or an aniline derivative can be used. Suitable for use in the present invention are phthalic anhydride, maleic anhydride, ethynyl aniline, and maleic anhydride is more preferred. The terminal blocking agent is used in an amount of from 0.001 to 1.0 mol per mol of the monomer component. The organic solvent to be used in the synthesis of the polyimine resin of the present invention is as long as it can dissolve any of the polyaminic acid as a raw material monomer and an intermediate product, or a polyamidene resin as a product. There is no particular limitation, and examples thereof include o-cresol, m-cresol, p-cresol ' N-methyl-2-pyrrolidone, N-ethin-2-pyrrolidone, N, N- Dimethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, cyclopentane, halogenated phenols, etc. These solvents may be used singly or in combination. The polar organic solvent may be used in an amount sufficient to dissolve the monomer to be fed, and generally contains 1 to 50% by mass of the solid component, and preferably 5 to 30% by mass. The polymerization reaction is carried out in an organic solvent while stirring and/or mixing, and is continuously carried out at a temperature ranging from 0 to 80 ° C for 1 to 30 hours, and then continuously at a temperature of from 100 to 300 ° C for 1 Torr. Minutes to 30 hours, if necessary, can divide the polymerization reaction or raise the temperature. In this case, the order of addition of the two reaction bodies is not particularly limited, but it is preferred to add an aromatic tetracarboxylic acid anhydride to the solution of the aromatic diamine. A closed loop catalyst can also be used in the present invention. Specific examples of the ring-closing catalyst used in the present invention include aromatic acids such as benzoic acid, o-benzoic acid, m-benzoic acid, p-benzene-20-201033251 formic acid, and fats such as trimethylamine and triethylamine. A trivalent amine; a heterocyclic tertiary amine such as isoquinoline, pyridine or β-picoline, etc., preferably using at least one amine selected from the group consisting of heterocyclic tertiary amines. The content of the closed-loop catalyst is preferably in the range of 0.01 to 10·00 in terms of the content of the closed-loop catalyst (mole) / the content of the poly-proline in the precursor (mol). A dehydrating agent can also be used in the present invention. For example, an aliphatic carboxylic anhydride such as acetic anhydride, propionic anhydride or butyric anhydride, or an aromatic carboxylic anhydride such as benzoic anhydride may be used, and it is not particularly limited as long as it can be effectively dehydrated. The content of the dehydrating agent is preferably in the range of 〇_〇1 to 10.00 in terms of the content of the dehydrating agent (mole) / the content of polyglycine (mol). In the present invention, a co-solvent can be used in order to azeotrope with water. Examples thereof include toluene, xylene, and the like, and are not particularly limited as long as they are effectively azeotroped with water. In the present invention, an additive may be added for the purpose of further improving the properties of the polyimide resin. These additives are various additives depending on the purpose, and are not limited to specific ones. Further, the addition method is not limited to a specific one in the addition period. Examples of the additive include metal oxides such as cerium oxide, titanium oxide, and aluminum oxide; and organic or inorganic additives such as phosphates such as calcium phosphate, calcium hydrogen phosphate, and calcium pyrophosphate. In the present invention, the reacted polyimine resin can be reprecipitated from the reaction solution with a suitable weak solvent. Examples of the weak solvent include acetone, methanol, ethanol, water, etc., and those which are effective for reprecipitation are not limited thereto. Further, the solvent for removing the reaction solvent remaining after reprecipitation is also not particularly limited, and it is preferred to use a solvent used for reprecipitation. In the present invention, the reaction solution may be used as a solution of a polyimide resin, or the re-precipitated polyimine resin may be redissolved in a solvent from the reaction solution to obtain a polyimide resin solution. In the case of the latter, it is not particularly limited as long as the polyimine resin can be effectively dissolved, and examples thereof include o-cresol, m-cresol, p-cresol, and N-methyl-2-pyrrolidone. , N·Ethyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl Organic solvents such as milled, γ-butyrolactone, cyclobutyl hydrazine, and halogenated phenols. In the present invention, the means for mixing the polyimine resin with the organic solvent is not particularly limited, and examples thereof include a method of mixing and stirring using a general stirring blade or a stirring blade for high viscosity; and using multiaxial extrusion. A method such as a machine or a static agitator; and further mixing and agitating using a high-viscosity mixer such as a roller honing machine. The composition of the polyimine resin in the polyimine resin solution obtained by the present invention is preferably, for example, preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. In this case, the viscosity is preferably 0.1 to 2000 Pa.s by the Brookfield viscometer, more preferably 1 to 1 Pa's, and it is preferable because the liquid can be stably supplied. The compound which generates an acid by irradiation with activating light which is used in the present invention is a sensitizer, and has a function of generating an acid and increasing solubility in a developing solution of a light-irradiating portion. The type thereof may, for example, be diazonaphthoquinone, an aryldiazolium salt, a diaryl iodine salt or a triarylsulfonium salt, and is not particularly limited to the case where the diazonaphthylquinone compound is highly sensitive. And better. -22- 201033251 Specific examples of the diazonaphthoquinone-based sensitizer include, for example, 1,2, naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide- 4-sulfonic acid low molecular hydroxybenzene, 2- and 4-methyl-phenol, 4,4'-hydroxy-propane ester, and the like. Other specific examples of the diazonaphthoquinone-based sensitizer may also be exemplified by a phenol compound and 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide. An ester of 4-sulfonic acid. These may be used alone or in combination of two or more. The amount of the compound which generates an acid upon irradiation with the activating light is, in terms of the allowable range of the sensitivity and the development time, is preferably from 1 to 50 parts by mass based on 100 parts by mass of the component (a). If it is less than 1 part by mass, it is difficult to obtain a good pattern, and when it exceeds 50 parts by mass, the sensitivity is liable to be greatly lowered. The positive photosensitive polyimide resin composition of the present invention may contain other additives such as a crosslinking agent, a plasticizer, a surfactant, a sensitizer, and an additive such as a promoter. The pattern forming method using the positive photosensitive polyimide resin composition of the present invention is formed by using the positive photosensitive polyimide resin composition of the present invention and forming a composition by the photolithography technique. A polyfluorene W imine film formed by quinone. In the pattern forming method of the present invention, first, a film using the positive photosensitive polyimide resin composition of the present invention is formed on the surface of a support substrate or the like. Further, in the pattern forming method using the positive photosensitive polyimide resin composition of the present invention, in order to improve the adhesion of the polyimide film to the support substrate, the surface of the support substrate may be treated with an auxiliary agent in advance. . The film formed of the polyimine is formed, for example, by forming a film of a positive photosensitive polyimide resin composition (hereinafter referred to as lacquer). The thickness of the polyimide film of the present invention -23-201033251 is not particularly limited, and it is preferable to form a film on the left and right sides, more preferably 3 μm or more, and particularly preferably a film thickness of 25 μm. In the positive photosensitive resin composition, when the blending ratio of the disazonaphthoquinone-based sensitizer is too small, the difference in solubility between the exposed portion and the non-exposed portion is too small to develop a pattern, and when it is too large, it is fearful of polyester. The membrane properties (toughness, linear thermal expansion coefficient, glass transition temperature, heat resistance, etc.) of the quinone imine polymer have adverse effects, and there is a major problem of film reduction after hardening. Therefore, the ratio is adjusted relative to the polymer. It is preferably from 5 to 40% by weight, more preferably from 20 to 40% by weight. The film forming step described above is preferably carried out at 120 ° C or lower. If it is at or above this temperature, the disazonaphthoquinone-based sensitizer may be thermally decomposed. For example, when a film is formed at 60 ° C, a large amount of a solvent remains in the coating film. At this time, pre-baking may be performed at 80 to 120 ° C for 1 to 30 minutes before the exposure operation. The polyimide film of the positive photosensitive polyimide composition is formed by the spin coating, dipping, and spray printing using the rotation of the positive photosensitive polyimide resin composition. The means such as screen printing are appropriately selected. Further, the film thickness of the film can be adjusted depending on the coating conditions, the solid content concentration of the composition, and the like. Further, the film formed on the support substrate may be peeled off from the support in advance, and a sheet made of polyimide may be adhered to the surface of the support substrate to form the film. Next, the formed film is irradiated with a mask of a predetermined pattern at room temperature (activated light such as ultraviolet light) for 1 second to 1 hour, and then the exposed portion is dissolved in an alkaline aqueous solution to remove the desired portion. Relief pattern (relief -24-201033251 pattern)» At this time, the residual film ratio after development is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. Further, the sensitivity is preferably 600 mJT/cm 2 or less, more preferably 500 mJ/cm 2 or less, and most preferably 4 50 mJ/cm 2 or less. The sensitivity here is the minimum necessary exposure amount in order to obtain a pattern having a high resolution of 10 μηη or less. The above alkaline aqueous solution is usually a solution in which a basic compound is dissolved in water. The basic compound may, for example, be a hydroxide or a carbonate of an alkali metal, an alkaline earth metal or an ammonium ion, an amine compound or the like. For example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, etc.; ethylamine, n-propylamine; triethylamine, methyl a tertiary amine such as diethylamine; an alcohol amine such as diethanolamine or triethanolamine; an aqueous solution of a quaternary ammonium salt such as tetramethylammonium hydroxide or tetraethyl hydroxide; and an appropriate amount added thereto. An aqueous solution of an aqueous solution of an alcohol such as methanol or ethanol or an aqueous solution of a surfactant. The development method may be in the form of a spray, a paddle, a dipping, an ultrasonic wave or the like. In most electronic devices, it is feared that residual metals may have adverse effects on electrical characteristics. Therefore, organic hydrazine is suitable, and an aqueous solution of tetramethylammonium hydroxide commonly used in the semi-conductive process is suitable. At this time, the concentration of the aqueous solution of tetramethylammonium hydroxide can be 5 to 10% by weight, preferably 0.1 to 5% by weight, and more preferably 2.38% by weight of the aqueous solution at room temperature for 1 〇 to 1 After a few minutes, clean with pure water to get a clear positive pattern. After the above development, it may be washed with water or a weak solvent as needed, and then dried at about 100 ° C, and it is expected that the pattern is stabilized. The film having the pattern is heated to obtain a film having excellent heat resistance, mechanical properties, and zero characteristics -25-201033251. When the conventional polyimide precursor is used, the pattern is 300 to 500 ° C. When the heating temperature is less than 300 ° C, the mechanical properties and thermal properties tend to decrease, such as a machine that exceeds the imine film. When the characteristics and the thermal characteristics are deteriorated, it is not necessary to heat the high temperature, and at most 200 ° C or so dry or low-boiling substances can be removed to form a heat-resistant polyimine pattern or the like. Bismuth imide film. The positive-type photosensitive polyimide resin of the present invention is an interlayer insulating film or the like of a surface protective film for electronic parts such as a semiconductor device. The surface protective film (protective layer film) using the positive photosensitive material of the present invention has no warpage of the substrate due to the subsequent coefficient of linear expansion or a positive photosensitive polyimide of the present invention. The semiconductor element of the resin composition edge film or the surface protection film is used to obtain the number of films of the semiconductor element having such high reliability (the average linear expansion coefficient of 40 ppm TC in the temperature range of 50 to 200 ° C is preferable) More preferably, it is 1 to 30 ppm/° C. The positive-type photosensitive polyimide resin composition of the present invention has an insulating layer or a surface protective film layer, and has excellent properties such as a cover film, a core, a color, a primer, and the like. [Examples] Hereinafter, the present invention is more specifically described by way of examples, and the present invention is not limited to the examples. Meanwhile, when the heating temperature in each of the examples is 40 ° C of the quinone film, In the case of the polypyrene, the composition of the dry low-linear expansion coefficient can be used at the temperature of the present invention, and the multilayer wiring board is excellent in polyetherimide resin property and is low-peeling, so that the interlayer obtained is extremely excellent. Coefficient of expansion) , to 层 to not only the layer, but as a guarantee. However, the present invention is characterized by the following method in addition to the above-mentioned method -26-201033251. 1 - Linear thermal expansion coefficient (CTE) of polyimine. For the polyimide of the measurement target, the wafer was broken and peeled off, and the expansion ratio was measured under the following conditions, and the measurement was carried out at 50 ° C to 65 ° C, 6 5 °C Yun 8 (jt's expansion rate per 15 °C / temperature, the measurement is carried out to 200 ° C, and the average enthalpy of measurement is calculated as CTE. Machine name: TMA4000S sample length manufactured by MAC Science :20mm ❹ Sample width: 2mm Starting load: 34.5g/mm2 Temperature at which temperature starts: 25°C Temperature at the end of temperature: 250°C Temperature increase rate: 5°C/min Gas environment: Argon 2. Residual film rate Calculate Λ Measure the film thickness after pre-baking treatment and the film thickness after development, and calculate the residual film ratio according to the following calculation method. Residual film rate (%) = {(film thickness after development) / (pre-bake Film thickness after treatment)}χ1 〇〇3. Sensitivity evaluation will be used to vividly form the minimum exposure amount required for the pattern of resolution 1 〇μιη as the sensitivity. Whether the resolution is clearly formed ίο μπι It is judged by microscopic observation of the relief pattern after exposure and development. The exposure amount is UV. Measurement test card and light meter (UV-M03: manufactured by OAK Co., Ltd.) -27- 201033251 4. Evaluation of the appearance of the film The appearance after development and after heat treatment was visually observed and observed under a microscope. If the unexposed part has no development residue and the pattern edge is smooth, it is evaluated as “good.” Moreover, the evaluation of the appearance after heat treatment “if the film is free of cracks, voids, peeling, cracking or warping of the wafer, etc.” is evaluated as “ (Synthesis Example 1) After replacing the inside of a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar with nitrogen gas, 2.13 g of 4,6-diaminodisorcinol hydrochloride was added, and anhydrous bis ( 4.58 g of trimellitic acid) phenyl ester and 2.08 g of triethylamine. Next, 50 g of N-methyl-2-pyrrolidone was added to completely dissolve the mixture, and the mixture was stirred at a reaction temperature of 25 ° C for 20 hours. A pale yellow polyaminic acid solution was obtained. Then, a Dean-stark trap was placed in the apparatus, and the mixture was stirred at a temperature of 200 ° C for 6 hours under a flow of N 2 gas. Start reprecipitation with acetone 200 ml. The product was pulverized in a mixer, and washed twice in acetone & 1000 ml at 25 ° C, and washed with stirring in 1000 ml of acetone for 6 hours under reflux, and dried at 70 ° C for 12 hours under reduced pressure to obtain a yield. 36.9 g of a pale yellow polyimine resin. Next, the obtained polyimine resin 100 g was mixed with 80 g of N-methyl-2-pyrrolidone and stirred at a temperature of 80 t for 1 hour, thereby obtaining a poly A solution of a quinone imine resin. This polyimine resin solution was used as lacquer-1. (Synthesis Example 2) The same procedure as in Synthesis Example 1 was carried out except that the diamine-based 4-aminosalicylic acid-p-aminophenyl ester was used, whereby the corresponding polyimine resin was dissolved. -28-201033251 liquid. This polyimine resin solution was used as Paint-2. (Synthesis Example 3) A corresponding polyimine resin solution was obtained in the same manner as in Synthesis Example 2, except that the anhydride was an anhydrous bis(trimellitic acid) decyl ester. This polyimine resin solution was used as paint-3. (Synthesis Example 4) The same procedure as in Synthesis Example 1 was carried out except that the anhydride was an anhydrous bis(trimellitic acid) benzoguanamine, whereby a corresponding polyimine resin solvent solution was obtained. This polyimine resin solution was used as lacquer-4. (Synthesis Example 5) The same operation as in Synthesis Example 2 was carried out except that the diamine was a 4-aminophenyl-41-amino group or a 3'-hydroxybenzoic acid ester, whereby the corresponding polyfluorene was obtained. Imine resin solution. This polyimine resin solution was used as lacquer-5. (Synthesis Example 6) The same operation as in Synthesis Example 1 except that the diamine was substituted with p-phenylenediamine for 4-aminosalicylic acid p-aminophenyl ester, whereby the polyimine resin y was reacted from the solution. Precipitate. Incapable of obtaining soluble polyimine (Synthesis Example 7) The same operation as in Synthesis Example 2 except that 4,4i-(2,2-hexafluoroisopropylidene)dicarboxylic acid dianhydride was used as the acid anhydride system. Thereby, the corresponding polyimine resin solution is obtained. This polyimine resin solution was used as paint-7. (Example 1) 2.00 g of a sensitizer NT-200 (Toyo Seiki Co., Ltd.) formed from an esterified quinone diazide compound was added to lacquer-1 at 90 ° C, and filtered to obtain a positive -29- 201033251 Type photosensitive polyimide resin composition. The positive photosensitive polyimide resin composition was spin-coated on a crucible wafer by a spin coater, and dried at 100 ° C for 10 minutes using a hot plate to obtain a coating film of ΙΟμηη. The coating film was passed through a mask (a residual pattern of 1 to 50 μ and a peeling pattern), and ultraviolet light was irradiated through the pattern mask using an ultrahigh pressure mercury lamp. Then development is carried out. The development system was carried out using a 2.38% aqueous solution of tetramethylammonium hydroxide. Then, it was washed with distilled water and dried. As a result, a good pattern was formed by irradiation with an exposure amount of 300 m J/cm 2 , and the residual film ratio was 90%. Moreover, the appearance after exposure is also good. Further, in a nitrogen atmosphere, heat treatment at 120 ° C / 15 minutes and 250 ° C / 60 minutes was carried out to obtain a tantalum wafer with a polyimide film which was free from warpage, cracking and peeling. Further, when the linear expansion coefficient of the polyimide film was measured by the above method, it was 10 〇 ppm / °C. (Examples 2 to 5) The same procedure as in Example 1 was carried out except that the paint 1 to 5 was used instead of the paint-1 used in Example 1, and the positive photosensitive polyimide resin © composition was adjusted. The same evaluation as in Example 1 was carried out, and the results thereof are shown in Tables (Comparative Examples 1 to 2) except that the lacquer-1 used in Example 1 was replaced by the polyimine and the varnish-7 of Synthesis Example 6, The positive photosensitive polyimide resin composition was adjusted in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1. -30- 201033251 [Table i] Linear thermal expansion coefficient (ppm wide C) Sensitivity (mJ/cm2) Residual film rate (%) Appearance after development Appearance after heat treatment Example 1 10 300 90 Good good 2 13 300 91 Good and good 3 15 360 89 Good good 4 17 320 90 Good good 5 13 300 89 Good good Comparative example 1 Unable to measure due to insolubility of polyimine 2 60 500 90 Good and good [Industrial Applicability] Positive type of the present invention The photosensitive polyimide resin composition is used as an electrical or electronic insulating material in the manufacture of a semiconductor device, and a surface protective film or an interlayer insulating film of a semiconductor device such as 1C or LSI is used. When it is used for the processing of fine patterns, there is no occurrence of water accompanying imidization, and there is no exposure to high temperature, and the coefficient of linear expansion is low, and the coefficient of linear expansion of the semiconductor wafer or the like of the substrate is close. There is no such thing as the warpage of the substrate by the separation of the substrate or the peeling of the film between the substrates, and it is meaningful for such applications. [Simplified illustration] None. [Main component symbol description] -31-

Claims (1)

201033251 VII. Patent Application Range: 1. A positive-type photosensitive polyimide resin composition's characteristics include: (a) a four-molecular ester bond represented by the following formula (Chemical Formula 1) a carboxylic acid dianhydride, a polyimine resin obtained by reacting an aromatic diamine represented by the formula (Chemical Formula 2) and/or an aromatic diamine represented by the formula (Chemical Formula 3), and an activated light irradiation And the compound that produces acid; [Chemical 1] [Chemical 2] (wherein Ri represents hydrogen, a carboxylic acid group, an alkyl group, a fluorine-substituted alkyl group, an alkoxy group or a halogen group; η represents an integer of 0 to 4, wherein n of 1 are the same or different substitutions Base; m means an integer greater than 1) -32- 201033251 [Chemical 3] (wherein A is selected from any of a group consisting of a group represented by -C(= 〇)〇-, -NHCCK; at least one of R2, R3 and r4 is a hydroxyl group, and the others A carboxylic acid group, an alkyl group, a fluorine-substituted alkyl group, an alkoxy group or a halogen group, which are the same or different groups; p, q, r and s represent an integer of 0 to 4, p + q + rgl '(s + 1) A's may be the same or different). 2. The positive photosensitive polyimide resin composition according to the first aspect of the invention, wherein the polyimine resin contains a repeating unit represented by (Chemical Formula 4), [Chemical 4] -33- 201033251 [〇5] (〇H)y Κ\.\βΗΗ2 k Re (wherein A is selected from the group consisting of -C( = 〇)〇_, -NHCO- Any of the bonding groups; R5, R6 represent an alkyl group, a fluorine-substituted alkyl group, an alkoxy group or a halogen group, which are the same or different groups; x, y represents an integer from 〇 to 4, x + Y21). 4. The positive-type photosensitive polyimide resin composition according to claim 1 or 2, wherein the structure of the formula (Chemical Formula 3) is a diamine represented by the following formula (Chemical Formula 6), [Chemical 6] (wherein A is selected from any of a group consisting of a group represented by -C(=0)0-, -NHCO-; and R5, R6 represents an alkyl group, a fluorine-substituted alkane. a group, an alkoxy group or a halogen group, which are the same or different groups; X, y represents an integer from 〇 to 4, X + ygl). 5. The positive photosensitive polyimide resin composition of any one of claims 1 to 4, wherein the acid is produced by irradiation with activated light - 34 - 201033251 is esterified Bismuth azide compound. 6. A polyimine imprint pattern, characterized in that the positive photosensitive composition according to any one of claims 1 to 5 is exposed to a pattern by activating light, and tetramethylammonium hydroxide is used. After development of alkaline water such as an aqueous solution, heat treatment is carried out at a temperature of 250 ° C or lower. 〇 ❹ -35- 201033251 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ y y\\\ V. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: [Chemical 1]