TW201714934A - Method for manufacturing cured film, method for manufacturing interlayer insulating film for rewiring layer, and method for manufacturing semiconductor device - Google Patents

Abstract

Provided is a method for manufacturing a cured film having an excellent corrosion resistance and chemical resistance. Further provided are a method for manufacturing an interlayer insulating film for a rewiring layer, and a method for manufacturing a semiconductor device that include the method for manufacturing a cured film. Disclosed in the present invention is a method for manufacturing a cured film having an amine content of 50 to 5,000 ppm, said method including the heating, at a temperature not exceeding a maximum heating temperature of 250 DEG C, a layer comprising a composition containing an amine-generating agent, with a polyimide precursor and/or a polybenzoxazole precursor.

Description

Method for producing cured film, method for producing interlayer insulating film for rewiring layer, and method for producing semiconductor device

The present invention relates to a method for producing a cured film, a method for producing an interlayer insulating film for a rewiring layer, and a method for producing a semiconductor device. More particularly, it relates to a method for producing a cured film using a heterocyclic-containing polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.

The thermosetting resin which is cyclized and hardened by polyimine or polybenzoxazole is excellent in heat resistance and insulation, and is used for an insulating layer of a semiconductor element or the like.

Further, since polyimide or the like has low solubility in a solvent, it is used in the state of a precursor (a heterocyclic-containing polymer precursor) before the cyclization reaction, and is applied to a substrate or the like, and then heated and The polymer precursor containing a heterocyclic ring is cyclized to form a cured film.

Here, Patent Document 1 discloses a polyimine precursor composition containing a polyimide precursor, a thermal base generator which generates a base due to heat, and a solvent, and a polyimide precursor. A polyamic acid or a thermal base generator which is a repeating unit of the following formula (1) is a neutral compound which generates a secondary amine by heating at a temperature of 200 ° C or lower to cause thermal decomposition. [Chemical 1] (wherein X represents a tetravalent organic group, Y represents a divalent organic group, and -COOH groups are in an ortho position with the -CONH group, respectively)

Further, Patent Document 2 discloses a polyamic acid composition comprising a polyphthalic acid, a polyaniline, a dopant for conducting conductivity of polyaniline, a solvent, and a basic additive. Made. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-056196 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2007-056182

[Problems to be Solved by the Invention] However, when a cured film obtained by cyclizing a heterocyclic-containing polymer precursor is used for an interlayer insulating film for a rewiring layer, etc., the cured film is resistant to corrosion and chemicals. Character is a problem. However, the inventors of the present invention have conducted research and found that the cured films described in the examples of Patent Document 1 and Patent Document 2 are inferior in corrosion resistance and chemical resistance. In order to solve the above problems, the present invention provides a method for producing a cured film excellent in corrosion resistance and chemical resistance. Further, the present invention relates to a method for producing an interlayer insulating film for a rewiring layer and a method for producing a semiconductor device, comprising the method for producing a cured film. [Means for solving the problem]

Based on the above, the inventors of the present invention have found that it is possible to provide a cured film having excellent corrosion resistance and chemical resistance by being manufactured so that the amount of amine of the cured film is within a predetermined range. this invention. Specifically, the problem is solved by the following means. <1> A method for producing a cured film, comprising: a layer having a composition comprising at least one of a polybenzazole precursor and a polybenzoxazole precursor and an amine generator at a maximum heating temperature of 250 ° C or less The temperature is heated, and the amine content of the cured film is from 50 ppm to 5,000 ppm. The method for producing a cured film according to the above aspect, wherein the amine generator is at least one of a photoamine generator and a hot amine generator. <3> The method for producing a cured film according to <1>, wherein the amine generator is a hot amine generator. The method for producing a cured film according to any one of <1> to <3> wherein the composition does not contain an amine having a pKa8 or higher of a conjugate acid. The method for producing a cured film according to any one of the above aspects, wherein the temperature from 20 ° C to 150 ° C to the maximum heating temperature is from 1 ° C / min to 10 ° C / min. The heating rate is performed at the temperature increase rate. <6> The method for producing a cured film according to <5>, wherein the heating is performed at the temperature increase rate, and after reaching the maximum heating temperature, heating is performed for 60 minutes to 240 minutes. The method for producing a cured film according to any one of <1> to <6> wherein the composition is based on a total amount of the polyimide intermediate and the polybenzoxazole precursor. The ratio of 0.01% by mass to 45% by mass includes the amine generator. The method for producing a cured film according to any one of the above aspects, wherein the polybenzazole precursor is represented by the following general formula (2), the polybenzoxazole The precursor is represented by the following general formula (3); general formula (2) [Chemical 2] In the formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom. Or a monovalent organic group; general formula (3) [chemical 3] In the formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. <9> The method for producing a cured film according to <8>, wherein in the formula (2), at least one of A ¹ and A ² is an oxygen atom, and among the R ¹¹³ and R ¹¹⁴ , the adjacent A R ¹¹³ and R ^{114 in which 1} and A ² are an oxygen atom represent a monovalent organic group; or in the formula (3), R ¹²¹ is a linear aliphatic group. The method for producing a cured film according to any one of <1> to <9> wherein the maximum heating temperature is from 160 ° C to 250 ° C. The method for producing a cured film according to any one of the above aspects, wherein the cured film has an amine content of from 500 ppm to 2,000 ppm. The method for producing a cured film according to any one of <1> to <11> wherein the composition further comprises a crosslinking agent. <13> The method for producing a cured film according to <12>, wherein the crosslinking agent has a molecular weight of from 100 to 800. The method for producing a cured film according to any one of the above aspects, wherein the amine generating agent is selected from the group consisting of an acidic compound which generates an amine when heated to 40 ° C to 250 ° C, and has a pKa1 of At least one of an anion of 0 to 4 and an ammonium salt of an ammonium cation. <15> The method for producing a cured film according to <14>, wherein the acidic compound is a compound which generates an amine when heated to 40 to 250 °C. <16> The method for producing a cured film according to <14>, wherein the acidic compound is a salt of an ammonium cation and a carboxylate anion. The method for producing a cured film according to any one of <1> to <16>, wherein the method for producing a cured film according to any one of <1> to <16>. The method of producing a cured film according to any one of <1> to <16>. <19> A cured film obtained by the method for producing a cured film according to any one of <1> to <16>. <20> A semiconductor device obtained by the method for producing a cured film according to any one of <1> to <16>. [Effects of the Invention]

According to the present invention, it is possible to provide a method for producing a cured film excellent in corrosion resistance and chemical resistance. Further, a method for producing an interlayer insulating film for a rewiring layer and a method for producing a semiconductor element including the method for producing the cured film can be provided.

The description of the constituent elements of the present invention described below may be carried out based on representative embodiments of the present invention, but the present invention is not limited to such an embodiment. In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, "actinic ray" means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (Extreme Ultraviolet (EUV) light), an X-ray, an electron beam, or the like. . Further, in the present invention, light means actinic rays or radiation. The "exposure" in this specification includes exposure using a mercury lamp, a far-ultraviolet light represented by a quasi-molecular laser, X-rays, EUV light, etc., using a particle beam such as an electron beam or an ion beam, unless otherwise specified. The depiction is also included in the exposure. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)allyl" means "allyl" and "(meth)acrylic acid" means either or both of "acrylic" and "methacrylic acid", "(meth)acrylic acid" "It means either or both of "acryloyl thiol" and "methacryl fluorenyl". In the present specification, the term "step" means not only an independent step, but even if it cannot be clearly distinguished from other steps, it is included in the term as long as the intended effect of the step is achieved. In the present specification, the solid content concentration means the mass percentage of the mass of the components other than the solvent with respect to the total mass of the composition. Further, the solid content concentration means a concentration at 25 ° C unless otherwise specified. In the present specification, Me represents a methyl group, Ac represents an ethyl group, and Ph represents a phenyl group.

The production method of the present invention is characterized by comprising: at least one of an amine comprising a polybenzazole precursor and a polybenzoxazole precursor (hereinafter sometimes referred to as "heterocyclic-containing polymer precursor") The layer of the composition of the generating agent is heated at a temperature at which the maximum heating temperature is 250 ° C or lower to produce a cured film having an amine content of 50 ppm to 5,000 ppm. By adjusting the amine content in this manner, it is possible to provide a cured film excellent in corrosion resistance and chemical resistance. Patent Document 1 discloses that an amine generated depending on the purpose of the cured film may remain in the cured film, but a specific amount is not clearly described. Further, Patent Document 2 discloses that the tertiary amine remaining in the cured film is preferably in the range of 1% by mass to 5% by mass. However, the relationship between the amount of amine in the cured film and the corrosion resistance and chemical resistance has not been studied at all. It should be surprising that the amine amount of the cured film contributes to the corrosion resistance and chemical resistance of the cured film. In the production method of the present invention, the amine content of the obtained cured film is preferably 100 ppm or more, more preferably 400 ppm or more, and still more preferably 500 ppm or more. The upper limit is preferably 2,000 ppm or less, more preferably 1,000 ppm. By setting it as such a range, it is excellent in corrosion resistance and chemical resistance. Further, it is preferred that the outgassing property is also excellent.

The method for producing a cured film of the present invention comprises heating a layer containing the composition at a maximum heating temperature of 250 ° C or lower. The layer comprising the composition is typically formed by applying the composition, preferably to a substrate. As a method of applying the composition to the substrate, spin coating, dipping, doctor blade coating, suspended casting, coating, spraying, electrostatic spraying, back roll coating, etc., can be uniformly applied. For the reason of the substrate, spin coating, electrostatic spraying, and reverse roll coating are preferred. For example, a layer containing the composition may be introduced into a temporary flexible carrier by a copper film printed circuit board by layer movement caused by buildup, and then applied to a final substrate.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material. Examples of the inorganic substrate include a glass substrate, a quartz substrate, a tantalum substrate, a tantalum nitride substrate, and a composite substrate obtained by vapor-depositing molybdenum, titanium, aluminum, copper, or the like on the substrate. Examples of the resin substrate include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, and poly. Bismuth, polyether oxime, polyarylate, allyl diglycol carbonate, polyamine, polyimine, polyamidimide, polyether phthalimide, polybenzoxazole, polyphenylene sulfide , polycycloolefin, norbornene resin, fluororesin such as polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, fluorenone resin, ionic polymer resin, cyanate resin, crosslinked antibutene A substrate of a synthetic resin such as an acid diester, a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound. These substrates are used in a small form as described above, and generally have a multilayered structure such as a thin film transistor (TFT) device depending on the form of the final product.

The amount of the applied composition (thickness of the layer) and the type of the substrate (the carrier of the layer) depend on the field of the intended use. The thickness of the layer is preferably in the range of 0.5 μm to 100 μm. It is preferred to apply the composition to the substrate and then dry it. Drying is preferably carried out, for example, at 60 ° C to 150 ° C for 10 seconds to 2 minutes.

The heating is carried out so that the maximum heating temperature becomes 250 ° C or lower. The upper limit of the maximum heating temperature is preferably 240 ° C or lower, more preferably 230 ° C or lower, still more preferably 220 ° C or lower, particularly preferably 210 ° C or lower, and more preferably 200 ° C or lower. The lower limit of the maximum heating temperature is preferably 140 ° C or higher, more preferably 160 ° C or higher, still more preferably 170 ° C or higher, and particularly preferably 180 ° C or higher. Here, the maximum heating temperature means that the sample undergoes a temperature of 30 seconds or more in the temperature experienced by the sample by heating for the cyclization reaction of the polymer precursor containing a hetero ring. The above temperature range is confirmed, and the highest temperature in the temperature range. The maximum heating temperature is preferably from 0 ° C to 100 ° C higher than the temperature at which the amine generating agent produces an amine, more preferably from 30 ° C to 60 ° C.

The heating is preferably carried out at a temperature increase rate of from 1 ° C / min to 10 ° C / min from a temperature of from 20 ° C to 150 ° C to a maximum heating temperature, and the temperature increase rate is more preferably from 2 ° C / min to 10 ° C / min, and further preferably It is preferably from 3 ° C / min to 8 ° C / min, particularly preferably from 3 ° C / min to 6 ° C / min. By setting the temperature increase rate to 1 ° C/min or more, productivity can be ensured and excessive evaporation of the amine can be prevented. By setting the temperature increase rate to 10 ° C / min or less, the residual stress of the cured film can be alleviated, and the amine can be prevented. Excessive residue. When heating at a low temperature of 250 ° C or lower at the highest heating temperature to cyclize and harden the heterocyclic-containing polymer precursor, it is difficult to adjust the amount of the amine in the cured film, but by a temperature of from 150 ° C or lower. Heating slowly at the temperature increase rate suppresses volatilization of the amine due to initial heating, and the amount of amine in the cured film can be easily adjusted. The temperature at the start of heating is preferably from 20 ° C to 150 ° C, more preferably from 20 ° C to 130 ° C, still more preferably from 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature of the layer containing the composition at the time of starting the heating to the highest heating temperature. For example, when the composition is applied onto a substrate and dried, the temperature after drying is preferably gradually increased from the boiling point of the solvent contained in the composition (30 to 200) °C. The heating is preferably carried out for 60 minutes to 240 minutes after reaching the maximum heating temperature, more preferably for 100 minutes to 230 minutes, and particularly preferably for 150 minutes to 220 minutes. By setting it as such a range, it becomes easier to adjust the amount of the amine in a hardened film.

Heating can be carried out in stages. As an example, a step of raising the temperature from 25 ° C to 180 ° C at 3 ° C / min, leaving at 180 ° C for 60 minutes, and then raising the temperature from 180 ° C to 200 ° C at 2 ° C / min, and at 200 ° C Place it for 120 minutes. In this case, it is preferred to set the heating conditions so that all of the stepwise heating satisfies the heating conditions. Further, it is also possible to perform cooling after heating, and the cooling rate in this case is preferably 1 ° C / min to 5 ° C / min.

In terms of preventing decomposition of a heterocyclic-containing polymer precursor such as polyfluorene, the heating step is preferably carried out in a low oxygen concentration environment by injecting an inert gas such as nitrogen, helium or argon. Go on. The oxygen concentration is preferably 50 ppm by volume or less, more preferably 20 ppm by volume or less.

As described above, the method for producing a cured film of the present invention preferably includes a step of applying (preferably, coating) the composition onto a substrate, and a layer (layer having a composition applied to the substrate). The composition of the composition) hardening step. In the present invention, in addition, a pattern forming step may be performed between the step of applying the composition on the substrate and the hardening step. The pattern forming step can be performed, for example, by photolithography. For example, the method performed by the exposure process and the process of performing a development process is mentioned. Regarding the pattern formation by photolithography, when it is a negative type, it is preferred to use a polymer precursor containing a hetero ring, a compound having an ethylenically unsaturated bond as a crosslinking agent, and photoradical polymerization. The photosensitive resin composition of the starting agent is used. Further, when it is a positive type, it is preferably carried out by using a photosensitive resin composition containing a polymer precursor containing a hetero ring and a photoacid generator. Further, when it is a negative type, the polymer precursor containing a hetero ring preferably has an ethylenically unsaturated bond. Details of these will be described later. Hereinafter, a case where pattern formation is performed by photolithography will be described. The step of applying (preferably, coating) the composition to the substrate and the step of hardening the layered composition applied to the substrate are the same as described above, and the preferred range is also the same.

<Exposure Step> In the exposure step, the actinic resin composition used for the substrate is irradiated with an actinic ray or a radiation of a predetermined pattern. The wavelength of the actinic ray or radiation varies depending on the composition of the photosensitive resin composition, but is preferably 200 nm to 600 nm, more preferably 300 nm to 450 nm. As the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generating device, or the like can be used, and i-ray (365 nm) can be preferably used. An actinic ray having a wavelength of 300 nm or more and 450 nm or less, such as h-ray (405 nm) or g-ray (436 nm). Further, the illumination light may be adjusted by a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter as needed. The exposure amount is preferably from 1 mJ/cm ² to 1,000 mJ/cm ² , more preferably from 200 mJ/cm ² to 800 mJ/cm ² . As the exposure device, mirror projection aligner, stepper, scanner, proximity, contact, microlens array, lens scanner, laser exposure, etc. can be used. Exposure machine. Further, when (meth) acrylate and the like olefin unsaturated compound are used, such photopolymerization is known as a film, especially in a thin layer due to oxygen in the air. This effect can be alleviated, for example, by a known prior method such as introduction of a temporary coating layer of polyvinyl alcohol or pre-exposure or pre-adjustment in an inert gas.

<Step of Performing Development Process> In the step of performing the development process, the unexposed portion of the photosensitive resin composition is developed using a developer. As the developer, an aqueous alkaline developer, an organic solvent or the like can be used. Examples of the basic compound used in the aqueous alkaline developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, and hemiplegia. Sodium, potassium metasilicate, ammonia or amine. Examples of the amine include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, and quaternary ammonium hydroxide. , Tetramethyl Ammonium Hydroxide (TMAH) or tetraethylammonium hydroxide. Among them, a basic compound containing no metal is preferred. Suitable aqueous alkaline developing solutions usually have a base of up to 0.5 N, but may also be suitably diluted prior to use. For example, an aqueous alkaline developing solution of about 0.15 N to 0.4 N, preferably 0.20 N to 0.35 N is also suitable. The basic compound may be used alone or in combination of two or more. When the basic compound is two or more kinds, it is preferred that the total is in the above range. As the organic solvent, the same solvent as that which can be used for the composition described later can be used. For example, acetic acid-n-butyl ester, γ-butyrolactone, cyclopentanone, and these may be mentioned.

<Polyimine precursor and polybenzoxazole precursor> The composition used in the present invention contains a polyimide precursor and a polybenzoxazole precursor (hereinafter, sometimes referred to as "heterocyclic-containing" At least one of a polymer precursor").

<<Polyimine precursor>> The polyimine precursor used in the present invention is not particularly limited as long as it can be polyiminated, and the main purpose thereof also includes a polyamidoximine precursor. Things. The polyimine precursor used in the present invention preferably contains a repeating unit represented by the following formula (2).

General formula (2) [Chemical 4] In the formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom. Or a monovalent organic base. A ¹ and A ² in the formula (2) each independently represent an oxygen atom or NH, and are preferably an oxygen atom. In particular, in order to more efficiently carry out cyclization at a low temperature, it is preferred that at least one of A ¹ and A ² is an oxygen atom, and R ¹¹³ and/or R ¹¹⁴ adjacent to A ¹ and A ^{2 which} are oxygen atoms are A monovalent organic base.

R ¹¹¹ represents a divalent organic group. The divalent organic group may, for example, be a linear or branched aliphatic group, a cyclic aliphatic group or a group containing an aryl group, and preferably a linear or branched fat having 2 to 20 carbon atoms. The group group, a cyclic aliphatic group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a group containing a combination of these is more preferably a group containing an aryl group having 2 to 60 carbon atoms. Examples of the aryl group include the following.

[Chemical 5] In the formula, A is preferably a single bond or a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ - and -NHCO-, and a group in the combination of these, more preferably a single bond, selected from alkyl groups having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)- a group in -S-, -SO ₂ -, and more preferably selected from -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) The divalent group in ₂ -.

More specifically, R ¹¹¹ may be a diamine residue remaining after the removal of the amine group of the diamine. Examples of the diamine include a linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Specifically, the diamine residue or the like remaining after the removal of the amine group of the following diamine is exemplified. Selected from 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2-diaminocyclopentane or 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane or 1,4-diamine Cyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane or 1,4-bis(aminomethyl)cyclohexane, Bis(4-aminocyclohexyl)methane, bis(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; M-phenylenediamine and p-phenylenediamine, diaminotoluene, 4,4'-diaminobiphenyl and 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane and 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl And 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide and 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodi Benzophenone and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4' -diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl) Propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4- Aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, double (3-Amino-4-hydroxyphenyl)indole, bis(4-amino-3-hydroxyphenyl)anthracene, 4,4'-diaminolated terphenyl, 4,4'-bis(4- Aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-( 2-aminophenoxy)phenyl]anthracene, 1,4-bis(4-aminophenoxy)benzene, 9,10-bis(4-aminophenyl)anthracene, 3,3'-di Methyl-4,4'-diaminodiphenylphosphonium, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1, 3-bis(4-aminophenyl)benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-di Aminodiphenylmethane, 4,4'-diamino octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4- (4-Aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroquinone, 3,3',4,4'-tetraaminobiphenyl , 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diamine Indole, 1,5-diaminopurine, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)anthracene, 4,4'-Dimethyl-3,3'-diaminodiphenylanthracene,3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4-di Amino cumene and 2,5-diamino cumene, 2,5-dimethyl-p-phenylenediamine, acetamidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldioxane, 2,7-diaminopurine, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diamino benzilanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1, 3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1,5-bis(4-aminophenyl)decafluoropentane 1,7-bis(4-aminophenyl)tetradecfluoroheptane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-dual [ 4-(2-Aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-bis(4-amino-2-trifluoromethyl) Phenoxy)benzene, 4 , 4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4 , 4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylphosphonium, 4,4'-bis(3-amino-5-trifluoromethylphenoxy)diphenyl Base, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3',5,5'-tetramethyl-4, 4'-Diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl And at least one diamine of biphenyl, 2,2',5,5',6,6'-hexafluorotoluidine and 4,4"'-diaminotetraben.

Further, examples of the diamine residue remaining after the removal of the amine group of the diamine (DA-1) to the diamine (DA-18) shown below are exemplified as R ¹¹¹ .

[Chemical 6]

[Chemistry 7]

Further, examples of the diamine residue remaining after the removal of the amine group of the diamine having two or more alkanediol units in the main chain are exemplified as R ¹¹¹ . It is preferably a diamine residue containing one or both of two or more ethylene glycol chains and propylene glycol chains in one molecule, more preferably a diamine residue containing no aromatic ring. As an example, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D- can be cited. 2000, D-4000 (above is the trade name, manufactured by HUNTSMAN (share)), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propane- 2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, etc., but is not limited thereto. The structures of Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176 are shown below.

[化8]

In the above, x, y, and z are average values.

R ¹¹⁵ represents a tetravalent organic group. The tetravalent organic group is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6). General formula (5) [Chemical 9] In the formula (5), R ¹¹² represents a single bond or a divalent group. The divalent group is preferably selected from the group consisting of a hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, and -NHCO-, and combinations thereof. base. R ^{112 is more} preferably a single bond or a divalent group selected from the group consisting of an alkylene group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- and -SO ₂ -. More preferably, it is a single bond or is selected from -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, and -SO ₂ - The divalent base in the composed group.

General formula (6) [10]

Specifically, examples of R ¹¹⁵ include a tetracarboxylic acid residue remaining after removing an anhydride group from a tetracarboxylic dianhydride. Specifically, a tetracarboxylic acid residue or the like remaining after removing an anhydride group from the following tetracarboxylic dianhydride can be mentioned. Selected from pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic acid Acid dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4 , 4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid Anhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Anhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl) Propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-double (2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, And the alkyl groups having 1 to 6 carbon atoms / Or at least one tetracarboxylic acid dianhydride derivative carbons, alkoxy of 1 to 6.

Further, examples of the tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride (DAA-1) to the tetracarboxylic dianhydride (DAA-5) shown below may be exemplified as R ¹¹⁵ . . [11]

From the viewpoint of the solubility of the alkaline developer, it is preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, as R ¹¹¹ , 2,2-bis(3-hydroxy-4-aminophenyl)propane and 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane are mentioned. , 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4- Hydroxyphenyl) hydrazine, bis(4-amino-3-hydroxyphenyl)fluorene, and (DA-1) to (DA-18) are preferred examples, and as R ¹¹⁵ , the above (DAA-) 1) to (DAA-5) are preferred examples.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. As the monovalent organic group represented by R ¹¹³ and R ¹¹⁴ , a substituent which enhances the solubility to the developing solution can be preferably used.

From the viewpoint of the solubility of the aqueous developing solution, R ¹¹³ and R ^{114 are} preferably a hydrogen atom or a monovalent organic group. The monovalent organic group may, for example, be an aryl group or an aralkyl group having one, two or three, preferably one, acidic groups bonded to a carbon atom of the aryl group. Specific examples thereof include an aryl group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic group is preferably an OH group. In terms of solubility in an aqueous developing solution, R ¹¹³ and R ¹¹⁴ are preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group.

From the viewpoint of the solubility of the organic solvent, R ¹¹³ and R ^{114 are} preferably a monovalent organic group. The monovalent organic group is preferably an alkyl group having a linear or branched shape, a cyclic alkyl group, or an aryl group, more preferably an alkyl group substituted with an aryl group. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a tetradecyl group. Base, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, borneol group, nonenyl group, decahydronaphthyl group, tricyclodecyl group, tetracyclodecyl group, and indenyl group. , dicyclohexyl, and decenyl. Among them, from the viewpoint of coexistence with high sensitivity, the cyclohexyl group is most preferable. Further, the alkyl group substituted with an aryl group is preferably a linear alkyl group substituted with an aryl group described later. Specific examples of the aryl group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a terpene ring, an anthracene ring, and a fused pentabenzene ring. , ethane naphthalene (acenaphthene) ring, phenanthrene ring, anthracene ring, thick tetraphenyl ring, Ring, triphenylene, anthracene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, pyridazine Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinoxaline ring, different Quinoline ring, carbazole ring, phenazin ring, acridine ring, phenanthroline ring, thioxan ring, benzopyran ring, xanthene ring, morphine ring, phenothiazine ring, and phenazine ring. The best is the benzene ring.

In the formula (2), at least one of R ¹¹³ and R ¹¹⁴ preferably has a polymerizable unsaturated group. Thereby, a negative photosensitive resin having better sensitivity and resolution can be obtained. By having a polymerizable unsaturated group (especially a radical polymerizable group) as described above, it is more effective in performing negative development on the cured film obtained by the production method of the present invention. However, in the case of performing negative development, when a crosslinking agent (particularly a radically polymerizable compound) is formulated, a polymerizable unsaturated group is not essential. Examples of the polymerizable unsaturated group include an epoxy group, an oxetanyl group, a group having an ethylenically unsaturated bond, a blocked isocyanate group, an alkoxymethyl group, a methylol group, and an amine group. Among them, in the case where the sensitivity is good, a group having an ethylenically unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III).

[化12]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, more preferably a methyl group. In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH(OH)CH ₂ - or a polyoxyalkylene group having 4 to 30 carbon atoms. Examples of suitable R ²⁰¹ include an exoethyl group, a propyl group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, and a hexamethylene group. Base, octamethylene, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, preferably ethyl, propyl, trimethylene, -CH ₂ CH(OH)CH ₂ -. More preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an exoethyl group.

When the repeating unit of the formula (2) contains a polymerizable group, the ratio of R ¹¹³ and R ¹¹⁴ to a polymerizable unsaturated group, and the polymerizable group: a molar group containing no polymerizable group is preferably 100:0 to 5 : 95, more preferably 100:0 to 20:80, and even more preferably 100:0 to 50:50.

When R ¹¹³ is a hydrogen atom in the formula (2), and/or R ¹¹⁴ is a hydrogen atom, the polyimine precursor may also form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond ( Counter salt). An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

Further, in the case of performing alkali development, the polyimine precursor preferably has a fluorine atom in the structural unit in terms of improving the resolution. By the fluorine atom, water repellency can be imparted to the surface of the film at the time of alkali development, thereby suppressing penetration from the surface and the like. The content of the fluorine atom in the polyimide precursor is preferably 10% by mass or more, and is preferably 20% by mass or less in terms of solubility in the alkaline aqueous solution.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized. Specific examples of the diamine component include bis(3-aminopropyl)tetramethyldioxane and bis(p-aminophenyl)octamethylpentaoxane.

Further, in order to enhance the storage stability of the composition, the polyimine precursor is preferably blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monofluorinated chlorine compound or a mono-active ester compound. Among these, it is more preferred to use a monoamine. Examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, and 1- Hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2- Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2- Carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-amine Salicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophene, 3-aminothiophene, 4-aminothiophene, and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of blocking agents.

The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (1-1). That is, at least one of the heterocyclic-containing polymer precursors used in the present invention is preferably a precursor having a repeating unit represented by the formula (1-1). By adopting such a structure, the width of the exposure latitude can be made wider. [Chemistry 13] In the formula (1-1), A ¹ and A ^{2 each} represent an oxygen atom, and R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. .

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ each independently have the same meanings as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in the formula (2), and the preferred ranges are also the same. R ¹¹² in the general formula (5) is the same meaning as R ^112, preferred ranges are also the same.

In the polyimine precursor, the repeating structural unit represented by the formula (2) may be one type or two or more types. Further, a structural isomer of a repeating unit represented by the formula (2) may also be contained. Further, in addition to the repeating unit of the above formula (2), the polyimine precursor may of course contain other kinds of repeating structural units.

As an embodiment of the polyimine precursor in the present invention, 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of all repeating units can be represented by the general formula (2). The repeating unit of the polyimine precursor.

The weight average molecular weight (Mw) of the polyimide precursor is preferably from 10,000 to 50,000, more preferably from 14,000 to 30,000. Further, the number average molecular weight (Mn) is preferably from 5,000 to 14,000. The degree of dispersion of the polyimide precursor is preferably 2.0 or more, more preferably 2.1 or more. The upper limit of the degree of dispersion of the polyimide precursor is not particularly limited, and is, for example, preferably 4.5 or less, more preferably 4.0 or less, still more preferably 3.8 or less, still more preferably 3.2 or less, still more preferably 3.1 or less. Further, it is preferably 3.0 or less, and particularly preferably 2.95 or less, and most preferably 2.6 or less.

<<Polybenzoxazole precursor>> The polybenzoxazole precursor used in the present invention is not particularly limited as long as it is a compound capable of polybenzoxazole, and the structure and the like are not particularly limited, and it is preferably The compound represented by the formula (3).

General formula (3) [Chemistry 14] In the formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group.

R ¹²¹ represents a divalent organic group. The divalent organic group may, for example, be an aliphatic group or an aryl group. Examples of the divalent aryl group include the following.

[化15] Wherein A represents a group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ - a divalent group in the group formed.

The divalent aliphatic group is preferably a linear aliphatic group in terms of promoting cyclization at a low temperature. The carbon number of the linear aliphatic group is preferably from 2 to 30, more preferably from 2 to 25, still more preferably from 3 to 20, still more preferably from 4 to 15, particularly preferably from 5 to 10. The linear aliphatic group is preferably an alkyl group. Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, and di-n-butylmalonic acid. Succinic acid, tetrafluoro succinic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, dimethyl methyl succinic acid, glutaric acid , hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl- 3-methylglutaric acid, adipic acid, octafluoroadipate, 3-methyladipate, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, ten Difluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-sebacic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecane Diacid, hexadecandioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, behenic acid, twenty-three Alkanoic acid, tetracosanedioic acid, dipentadecanedioic acid, hexadecanedioic acid, heptacosanedioic acid, octacosanedioic acid, octadecanedioic acid, triacontane Acid, three A dodecanedioic acid, tris dodecanedioic acid, diglycolic acid, and the dicarboxylic acid represented by the following formula.

[Chemistry 16] (wherein Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6)

R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in the above formula (2), and the preferred range is also the same. Further, R ^{122 is} preferably a residue of a bisaminophenol derivative represented by the following formula (A). Ar(NH ₂ ) ₂ (OH) ₂ (A) wherein Ar is an aryl group.

Examples of the bisaminophenol derivative of the above formula (A) include 3,3'-diamino-4,4'-dihydroxybiphenyl and 4,4'-diamino-3. 3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 4,4'-diamino-3,3'-dihydroxydiphenylanthracene, Bis(3-amino-4-hydroxyphenyl)methane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl) Hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, bis(4-amino-3-hydroxyphenyl)methane, 2,2-bis(4-amine) 3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxydiphenyl Ketone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamine Base-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, and the like. These bisaminophenols may be used singly or in combination of two or more.

Among the bisaminophenol derivatives represented by the formula (A), a bisaminophenol derivative having the following aryl group is preferred.

[化17] In the formula, X ₁ represents -O-, -S-, -C(CF ₃ ) ₂ -, -CH ₂ -, -SO ₂ -, -NHCO-. Further, in the above structure, -OH and -NH ₂ contained in the structure of the general formula (A) are bonded to each other in the ortho position (adjacent position). In view of obtaining a benzoxazole precursor which is highly transparent to i-rays and hardens at a low temperature, the bisaminophenol derivative of the formula (A) preferably has the following formula Bisphenol represented by (As).

[化18] (As)

Wherein R ₁ is an alkylene group, a substituted alkylene group, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, a single bond, or is selected from the group consisting of the following formula (A- The organic group in the group of sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, a decyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, a decyloxy group, or a cyclic alkyl group, and may be the same or different.

[Chemistry 19] (A-sc) (wherein * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the formula (As))

In the above formula (As), it is considered that the ortho position of the phenolic hydroxyl group, that is, the substituent on R ₃ , causes the distance between the carbonyl carbon of the guanamine bond and the hydroxyl group to be closer, and becomes high cyclization upon hardening at a low temperature. The effect of the rate is further improved in terms of further improvement.

Further, in the formula (As), the effect of maintaining high transparency to i-rays and high cyclization rate upon hardening at low temperatures is obtained, and at the same time, sufficient solubility is obtained when an alkaline aqueous solution is used for a developing solution. In the aspect of the polybenzoxazole precursor excellent in balance, it is particularly preferred that R ₂ is an alkyl group and R ₃ is an alkyl group.

Further, in the formula (As), R ₁ is preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group in R ₁ include -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CH _{2 )} CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ )(CH ₂ CH ₃ )-, -CH(CH ₂ CH ₂ CH ₃ )-, -C( CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -CH(CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH(CH ₃ ) ₂ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH(CH ₂ CH(CH ₃ ) ₂ )-, -C(CH ₃ )(CH ₂ CH(CH _{3 ) 2} )-, -CH(CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -CH(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ )-, etc., wherein high transparency for i-rays and hardening at low temperatures can be obtained It is more preferably -CH ₂ -, -CH in terms of a polybenzoxazole precursor which is effective not only for an alkaline aqueous solution but also for a solvent and has a sufficient solubility for a solvent. (CH ₃ )-, -C(CH ₃ ) ₂ -.

As a method for producing the bisaminophenol derivative represented by the above formula (As), for example, paragraphs 0085 to 0094 and 1 (paragraph 0189 of JP-A-2013-256506) can be referred to. Paragraph No. 0190), the contents of which are incorporated in this specification.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (As) include those described in paragraph number 0070 to paragraph 0080 of JP-A-2013-256506. Into this specification. Of course, it is not limited to these specific examples.

Among them, the bisaminophenol derivative represented by the above formula (A-s) is preferably as described below.

[Chemistry 20]

R ¹²³ and R ¹²⁴ represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a polymerizable unsaturated group. In terms of obtaining a negative photosensitive resin having better sensitivity and resolution, at least one of R ¹²³ and R ¹²⁴ preferably represents a polymerizable unsaturated group. The polymerizable unsaturated group is the same as the one described in R ¹¹³ and R ¹¹⁴ in the formula (2), and the preferred range is also the same.

The polybenzoxazole precursor may contain other kinds of repeating structural units in addition to the repeating unit of the above formula (3). In terms of suppressing the occurrence of warpage accompanying the ring closure, it is preferred to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

[Chem. 21] In the general formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ^2s is a hydrocarbon group having 1 to 10 carbon atoms, and R ^3s , R ^4s , R ^5s and R At least one of ^6s is an aryl group, and the remainder is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the molar % of the Z portion, the a structure is 5 mol% to 95 mol%, the b structure is 95 mol% to 5 mol%, and a+b is 100 mol%.

In the general formula (SL), preferred examples of Z include those in which R ^5s and R ^6s in the b structure are phenyl groups. Further, the molecular weight of the structure represented by the general formula (SL) is preferably from 400 to 4,000, more preferably from 500 to 3,000. The molecular weight can be determined by gel permeation chromatography which is usually used. By setting the molecular weight to the above range, the effect of suppressing warpage and the effect of improving solubility can be reduced by reducing the elastic modulus after dehydration ring closure of the polybenzoxazole precursor.

When the diamine residue represented by the general formula (SL) is contained as another kind of repeating structural unit, in terms of enhancing alkali solubility, it is preferred to further include the removal of the anhydride group from the tetracarboxylic dianhydride. The remaining tetracarboxylic acid residue serves as a repeating structural unit. Examples of such a tetracarboxylic acid residue include an example of R ¹¹⁵ in the formula (2).

Further, in order to further enhance the storage stability of the composition, it is preferred to use an acid anhydride to block the amine group at the terminal of the polybenzoxazole precursor, which comprises at least one alkenyl group or alkynyl group. An aliphatic group or a cyclic group.

Examples of such a group derived from an acid anhydride, that is, a terminal group, may be, for example, a group having an aliphatic group or a cyclic group having at least one alkenyl group or alkynyl group reacted with an amine group. base. These may be used alone or in combination of two or more.

[化22]

[化23]

In particular, in terms of improving the preservability, the base shown below is preferred.

[Chem. 24]

For example, a bisaminophenol derivative represented by the formula (A), a dicarboxylic acid selected from the group consisting of R ¹²¹ , a dicarboxylic acid dichloride of the dicarboxylic acid, a dicarboxylic acid derivative, etc. The compound in the reaction is reacted to obtain a polybenzoxazole precursor. Further, when a dicarboxylic acid is used, an active ester type dicarboxylic acid derivative obtained by previously reacting 1-hydroxy-1,2,3-benzotriazole or the like may be used in order to increase the reaction yield and the like.

For example, when used in the composition described later, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably from 8,000 to 30,000, more preferably from 9,000 to 29,000, still more preferably from 10,000 to 28,000. Further, the number average molecular weight (Mn) is preferably from 5,000 to 14,000, more preferably from 6,000 to 12,000, still more preferably from 6,500 to 11,200. The degree of dispersion of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, still more preferably 1.6 or more. The upper limit of the degree of dispersion of the polybenzoxazole precursor is not particularly limited, and is, for example, preferably 2.6 or less, more preferably 2.5 or less, still more preferably 2.4 or less, still more preferably 2.3 or less, still more preferably 2.2. the following.

The content of the heterocyclic-containing polymer precursor in the composition used in the present invention is preferably from 20% by mass to 50% by mass, and more preferably from 25% by mass to 40% by mass. Further, the content of the heterocyclic-containing polymer precursor in the composition used in the present invention is preferably 70% by mass or more, and more preferably 75% by mass or more based on the solid content of the composition. The upper limit is not particularly limited, and the total amount of the heterocyclic-containing polymer precursor and the amine generator may be 100% by mass of the solid content of the composition. Further, the composition used in the present invention may contain only one type of polymer precursor containing a hetero ring, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is the said range. Further, both the polyimine precursor and the polybenzoxazole precursor may be contained, but more preferably one or more polyimine precursors are contained, and only two or more polyphenyls are contained. And the morphology of the oxazole precursor.

<Amine Producer> The composition used in the present invention contains an amine generator. As the amine generating agent in the present invention, a reaction which does not exhibit an amine generation at normal temperature and normal pressure (for example, 25 ° C, 101, 325 Pa) can be widely used, but an amine is produced by decomposition or structural transformation by a certain stimulus. Here, as for the stimuli, it is exemplified that the amine (hot amine generator) is produced by decomposition or structural transformation by heating (preferably the heating) at a certain temperature or higher, and irradiation (exposure) by light Decomposition or structural transformation to produce an amine (photoamine generator). As the stimulus other than this, a stimulus based on a reaction with an active species selected from an acid × base × radical, or a reaction with an oxidizing agent or a reducing agent can be exemplified. In the present invention, the amine generating agent is preferably a hot amine generating agent and a photoamine generating agent, more preferably a hot amine generating agent.

Examples of the amine generators include amines which are passivated by a protecting group such as an alkoxycarbonyl group, nifedipines, salts formed of an amine and an acid, and quaternary ammonium salts. . By blending such a compound, the cyclization reaction of the heterocyclic-containing polymer can be carried out at a low temperature, and a composition having more excellent stability can be formed. Further, the amine generator used in the present invention does not produce an amine unless it is stimulated, so that even if it is coexisted with a heterocyclic-containing polymer precursor, the ring of the heterocyclic-containing polymer precursor during storage can be suppressed. It has excellent storage stability.

<<Thermal amine generator>> The type of the heat amine generator is not particularly limited, and is preferably an acidic compound (A1) selected from the group consisting of heating to 40 ° C to 250 ° C to produce an amine, and having a pKa1 of 0. At least one of an anion of ～4 and an ammonium salt (A2) of an ammonium cation. By using such a compound, the outgassing property can be further improved. Here, pKa1 represents a logarithmic mark (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polybasic acid. By compounding such a compound, the cyclization reaction of the heterocyclic-containing polymer precursor can be carried out at a low temperature, and a composition having more excellent stability can be formed. Further, since the hot amine generating agent does not generate an alkali without heating, even if it coexists with the polymer precursor containing a hetero ring, cyclization of the heterocyclic-containing polymer precursor during storage can be suppressed, and storage stability can be prevented. Excellent.

When the hot amine generating agent is heated to generate a base, the cyclization reaction of the heterocyclic-containing polymer precursor can be promoted by the base generated from the compounds, and the heterocyclic-containing polymer can be carried out at a low temperature. Cyclization of the precursor. Further, even if these compounds are coexisted with a heterocyclic-containing polymer precursor which is cyclized and cured by an amine, the cyclization of the polymer precursor containing a hetero ring is hardly obtained unless heating is performed. This is carried out, so that a composition excellent in stability can be prepared. In the present specification, the term "acid compound" means a compound obtained by extracting 1 g of the compound into a container and adding a mixture of ion-exchanged water and tetrahydrofuran (mass ratio of water/tetrahydrofuran = 1/4) 50 mL. The mixture was stirred at room temperature for 1 hour, and the value obtained by measuring the solution at 20 ° C was less than 7 using a pH (potential hydrogen) meter.

The amine generating temperature of the hot amine generating agent in the present invention is preferably from 40 ° C to 250 ° C, more preferably from 120 ° C to 250 ° C. The upper limit of the temperature at which the amine is produced is more preferably 240 ° C or less, more preferably 230 ° C or less, still more preferably 220 ° C or less, still more preferably 200 ° C or less, still more preferably 190 ° C or less, and particularly preferably 180 ° C or less. . The lower limit of the temperature at which the amine is produced is more preferably 130 ° C or higher, and particularly preferably 135 ° C or higher. The amine production temperature can be measured by differential scanning calorimetry, and the hot amine generating agent is heated to 250 ° C at 5 ° C / min in a pressure resistant capsule, the peak temperature of the lowest heat generating peak is read, and the peak temperature is taken as the amine generating temperature. To carry out the measurement. When the temperature at which the amine produced by the heat amine generator is 40° C. or more, it is difficult to produce an amine during storage, and thus a composition having more excellent stability can be prepared. If the temperature at which the amine produced by the heat amine generator is 250 ° C or lower, the cyclization temperature of the polymer precursor containing the hetero ring can be lowered.

In the present invention, the amine produced by the hot amine generating agent is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since the tertiary amine has a high basicity, the cyclization temperature of the heterocyclic-containing polymer precursor can be further lowered. Further, the boiling point of the amine produced by the hot amine generating agent is preferably 80 ° C or higher, more preferably 100 ° C or higher, and still more preferably 140 ° C or higher. Further, the molecular weight of the produced amine is preferably from 60 to 300. The lower limit is more preferably 100 or more, and still more preferably 120 or more. The upper limit is preferably 250 or less, and more preferably 200 or less. Further, the value of the molecular weight is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) preferably contains one or more selected from the group consisting of an ammonium salt and a compound represented by the formula (1A) to be described later.

In the present invention, the ammonium salt (A2) is preferably an acidic compound. Further, the ammonium salt (A2) may be a compound containing an acidic compound which generates an amine when heated to 40 ° C to 250 ° C (preferably 120 ° C to 200 ° C), or may be heated to 40 ° C if not contained. A compound which produces an acidic compound of an amine at -250 ° C (preferably 120 ° C to 200 ° C).

<<Ammonium salt>> In the present invention, the ammonium salt refers to a salt of an ammonium cation represented by the formula (11) or the formula (12) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond or may be present outside the molecule of the ammonium cation, preferably outside the molecule of the ammonium cation. Further, the fact that the anion is present outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extra-molecular anion of the cation portion is also referred to as a counter anion. [化25] In the general formulae (11) and (12), R ^1N to R ^6N each independently represent a hydrogen atom or a hydrocarbon group, and R ^7N represents a hydrocarbon group. R ^1N and R ^2N , R ^3N and R ^4N , R ^5N and R ^6N , and R ^5N and R ^7N may each bond to form a ring.

In the present invention, the ammonium salt is preferably an anion having an pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is more preferably 3.5 or less, still more preferably 3.2 or less. The lower limit is more preferably 0.5 or more, and still more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the heterocyclic-containing polymer precursor can be cyclized at a low temperature, and the stability of the composition can be improved. When pKa1 is 4 or less, the stability of the heat amine generating agent is good, and it is possible to suppress the occurrence of an amine without heating, and the stability of the composition is good. When pKa1 is 0 or more, the produced amine is hardly neutralized, and the cyclization efficiency of the heterocyclic-containing polymer precursor is good. The type of the anion is preferably one selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and the carboxylate anion is more preferable because the stability of the salt and the thermal decomposition are coexisting. . That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion. The carboxylate anion is preferably an anion of a divalent or higher carboxylic acid having two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. According to this aspect, a hot amine generator which can further improve the stability, hardenability, and developability of the composition can be obtained. In particular, by using an anion of a divalent carboxylic acid, the stability, hardenability, and developability of the composition can be further improved. In the present invention, the carboxylate anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and still more preferably 3.2 or less. According to this aspect, the stability of the composition can be further improved. Here, pKa1 represents the logarithm of the reciprocal of the first dissociation constant of the acid, and can be referred to as "Determination of Organic Structures by Physical Methods" (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; Editor: Braude, EA, Nachod, FC; American Academic Press (New York, 1955), or "Data for Biochemical Research" (author: Dawson) , RMC, et al; Oxford, Clarendon Press, 1959). For the compounds not described in these documents, a value calculated by a structural formula using ACD/pKa (manufactured by ACD/Labs) was used.

In the present invention, the carboxylate anion is preferably represented by the formula (X1). [Chem. 26] In the formula (X1), EWG represents a pull electron group.

In the present invention, the electron withdrawing group means that the substituent constant σm of Hammett shows a positive value. Here, σm is described in detail in the general theory of Tono Hiroshi, "Organic Synthetic Chemistry Association", Vol. 23, No. 8 (1965) P.631-642. Further, the electron withdrawing group of the present invention is not limited to the substituents described in the literature. Examples of the substituent having a positive value of σm include a CF ₃ group (σm = 0.43), a CF ₃ CO group (σm = 0.63), a HC ≡ C group (σm = 0.21), and a CH ₂ = CH group ( Σm=0.06), Ac group (σm=0.38), MeOCO group (σm=0.37), MeCOCH=CH group (σm=0.21), PhCO group (σm=0.34), H ₂ NCOCH ₂ group (σm=0.06), etc. . Further, Me represents a methyl group, Ac represents an ethyl group, and Ph represents a phenyl group.

In the present invention, EWG preferably represents a group represented by the following formula (EWG-1) to formula (EWG-6). [化27] In the formula, R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aryl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. As a substituent, a carboxyl group is preferable. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. As a substituent, a carboxyl group is preferable. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. As a substituent, a carboxyl group is preferable.

In the present invention, the carboxylate anion is also preferably represented by the following formula (X). [化28] In the formula (X), L ¹⁰ represents a single bond, or a divalent linking group selected from the group consisting of an alkyl group, an alkenyl group, an extended aryl group, -NR ^X - and a combination thereof, and R ^X represents hydrogen. Atom, alkyl, alkenyl or aryl.

The carbon number of the alkylene group represented by L ¹⁰ is preferably from 1 to 30, more preferably from 1 to 20, still more preferably from 1 to 10. The alkylene group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The alkylene group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. The carbon number of the alkenyl group represented by L ¹⁰ is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. The carbon number of the aryl group represented by L ¹⁰ is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have.

The alkyl group represented by R ^X preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. The number of carbon atoms of the alkenyl group represented by R ^X is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have. The carbon number of the aryl group represented by R ^X is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion. These specific examples can be preferably used.

The ammonium cation is preferably represented by any one of the formulae (Y1-1) to (Y1-6). [化29]

In the formula, R ¹⁰¹ represents an n-valent organic group, R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group, and R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring, and Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

R ¹⁰¹ represents an n-valent organic group. The monovalent organic group may, for example, be an alkyl group, an alkylene group or an aryl group. Examples of the divalent or higher organic group include one in which one or more hydrogen atoms are removed from the monovalent organic group to form an n-valent group. R ^{101 is} preferably an aryl group. Specific examples of the aryl group include those described in Ar ¹⁰ to be described later.

R ¹⁰² to R ¹¹¹ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁵⁰ and R ¹⁵¹ each independently represent a hydrocarbon group. The hydrocarbon group represented by R ¹⁰² to R ¹¹¹ , R ¹⁵⁰ and R ¹⁵¹ is preferably an alkyl group, an alkenyl group or an aryl group. The alkyl group, the alkenyl group and the aryl group may further have a substituent. The substituent may be mentioned as a substituent which the organic group represented by A ¹ mentioned later may have.

The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent or may be unsubstituted. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The alkenyl group may have a substituent or may be unsubstituted. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted.

Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12. The aryl group may have a substituent or may be unsubstituted.

R ¹⁰⁴ and R ¹⁰⁵ , R ¹⁰⁴ and R ¹⁵⁰ , R ¹⁰⁷ and R ¹⁰⁸ , and R ¹⁰⁹ and R ¹¹⁰ may be bonded to each other to form a ring. Examples of the ring include a cyclic aliphatic (non-aromatic hydrocarbon ring), an aromatic ring, and a hetero ring. The ring may be a single ring or a multiple ring. The linking group when the group is bonded to form a ring may be selected from the group consisting of -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and a combination thereof. A divalent linkage in the group. Specific examples of the ring to be formed include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiophene ring. a azine ring, an anthracene ring, an isoindole ring, a benzimidazole ring, an anthracene ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, A porphyrin ring, an oxazole ring, and the like.

In the present invention, the ammonium cation is preferably a structure represented by the formula (Y1-1) or the formula (Y1-2), more preferably represented by the formula (Y1-1) or the formula (Y1-2), R ¹⁰¹ The structure of the aryl group is particularly preferably a structure represented by the formula (Y1-1) and R ¹⁰¹ is an aryl group. That is, in the present invention, the ammonium cation is preferably represented by the following formula (Y). [化30] In the general formula (Y), Ar ¹⁰ represents an aryl group, and R ¹¹ to R ¹⁵ each independently represent a hydrogen atom or a hydrocarbon group, and R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring, and n represents an integer of 1 or more.

Ar ¹⁰ represents an aryl group. Specific examples of the aryl group include a substituted or unsubstituted benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a terpene ring, an anthracene ring, and a fused pentabenzene. Ring, ethane naphthalene ring, phenanthrene ring, anthracene ring, thick tetraphenyl ring, Ring, triphenylene, anthracene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, pyridazine Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinoxaline ring, different Quinoline ring, carbazole ring, phenazin ring, acridine ring, phenanthroline ring, thioxan ring, benzopyran ring, xanthene ring, morphine ring, phenothiazine ring, and phenazine ring. Among them, from the viewpoint of storage stability and high sensitivity, a benzene ring, a naphthalene ring, an anthracene ring, a phenothiazine ring, or an oxazole ring is preferred, and a benzene ring or a naphthalene ring is preferred. Examples of the aryl group may have a substituent group, A ¹ described later include an organic group represented by may have a substituent group as those described.

R ¹¹ and R ¹² each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is not particularly limited, and is preferably an alkyl group, an alkenyl group or an aryl group. R ¹¹ and R ^{12 are} preferably a hydrogen atom.

The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a tetradecyl group. Base, octadecyl, isopropyl, isobutyl, t-butyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include adamantyl group, norbornyl group, borneol group, nonenyl group, decahydronaphthyl group, tricyclodecyl group, tetracyclodecyl group, and indenyl group. , dicyclohexyl and decenyl. Among them, from the viewpoint of coexistence with high sensitivity, the cyclohexyl group is most preferable. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be linear, branched or cyclic, and is preferably linear or branched, and more preferably linear. The carbon number of the aryl group is preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 6 to 12.

R ¹³ to R ¹⁵ represent a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include the hydrocarbon groups described in the above R ¹¹ and R ¹² . R ¹³ to R ^{15 are} particularly preferably an alkyl group, and a preferred embodiment is also the same as those described for R ¹¹ and R ¹² .

R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring. Examples of the ring include a cyclic aliphatic group (non-aromatic hydrocarbon ring), an aromatic ring, and a hetero ring. The ring may be a single ring or a multiple ring. Examples of the linking group when R ⁴ and R ⁵ are bonded to each other to form a ring include -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aryl group, and a combination thereof. A divalent linking group in the group formed. Specific examples of the ring to be formed include a pyrrolidine ring, a pyrrole ring, a piperidine ring, a pyridine ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, a pyrazine ring, a morpholine ring, and a thiophene ring. a azine ring, an anthracene ring, an isoindole ring, a benzimidazole ring, an anthracene ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, A porphyrin ring, an oxazole ring, and the like.

R ¹³ to R ^{15 are} preferably a ring in which R ¹⁴ and R ¹⁵ are bonded to each other to form a ring, or R ¹³ is a linear alkyl group having 5 to 30 carbon atoms (more preferably 6 to 18 carbon atoms), R ¹⁴ and R ^{15 .} Each is independently an alkyl group having 1 to 3 carbon atoms (more preferably 1 or 2 carbon atoms). According to this aspect, an amine species having a high boiling point can be easily produced. Further, from the viewpoint of the basicity or boiling point of the amine species to be produced, R ¹³ to R ^{15 are} preferably a total of 7 to 30, more preferably 10 to 20 carbon atoms of R ¹³ and R ¹⁴ and R ¹⁵ . . Further, the reason for the fact that the amine group having a high boiling point is likely to be generated is preferably a chemical formula of "-NR ¹³ R ¹⁴ R ¹⁵ " in the formula (Y) of from 80 to 2,000, more preferably from 100 to 500.

On the other hand, as an embodiment for further improving the adhesion to the copper wiring, in the general formula (Y), R ¹³ and R ¹⁴ are a methyl group or an ethyl group, and R ¹⁵ is a carbon number. 5 or more linear, branched or cyclic alkyl groups or aryl groups. In the present embodiment, R ¹³ and R ¹⁴ are preferably a methyl group, and R ¹⁵ is a linear alkyl group having 5 to 20 carbon atoms, a branched alkyl group having 6 to 17 carbon atoms, or a ring having 6 to 10 carbon atoms. More preferably, R ¹³ and R ¹⁴ are a methyl group, R ¹⁵ is a linear alkyl group having 5 to 10 carbon atoms, a branched alkyl group having 6 to 10 carbon atoms, or a carbon number of 6 to 8. Cyclic alkyl or phenyl. By thus reducing the hydrophobicity of the amine species, even when the amine is attached to the copper wiring, the affinity between the copper surface and the polyimide may be more effectively suppressed. In the present embodiment, the preferred ranges of Ar ¹⁰ , R ¹¹ , R ¹² and n are the same as described above.

<<<Compound represented by the general formula (1A)>>> In the present invention, the acidic compound is preferably a compound represented by the following formula (1A). This compound is acidic at room temperature, but disappears by heating, carboxy decarbonation or dehydration cyclization, whereby the amine moiety which has been previously neutralized and deactivated becomes active, thereby becoming alkaline. Hereinafter, the general formula (1A) will be described.

General formula (1A) [Chem. 31] In the formula (1A), A ¹ represents a p-valent organic group, R ¹ represents a monovalent organic group, L ¹ represents an (m+1)-valent organic group, m represents an integer of 1 or more, and p represents 1 or more. The integer.

In the formula (1A), A ¹ represents a p-valent organic group. The organic group may, for example, be an aliphatic group or an aryl group, and is preferably an aryl group. By setting A ¹ as an aryl group, it is easy to produce an amine having a high boiling point at a lower temperature. By increasing the boiling point of the produced amine, volatilization or decomposition by heating during curing of the heterocyclic-containing polymer precursor can be suppressed, and cyclization of the heterocyclic-containing polymer precursor can be more efficiently performed. Examples of the monovalent aliphatic group include an alkyl group and an alkenyl group. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain. The alkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and an adamantyl group. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 10. The alkenyl group may be any of a linear chain, a branched chain, and a cyclic chain. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth)allyl group. Examples of the divalent or higher aliphatic group include a group in which one or more hydrogen atoms are removed from the monovalent aliphatic group. The aryl group may be a single ring or a polycyclic ring. The aryl group may also be a heteroaryl group containing a hetero atom. The aryl group may have a substituent or may be unsubstituted. It is preferably unsubstituted. Specific examples of the aryl group include a benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a terpene ring, an anthracene ring, a fused pentene ring, a terpene ring, and a phenanthrene ring. , anthracene ring, thick tetraphenyl ring, Ring, triphenylene, anthracene, biphenyl, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, pyridazine Ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizine ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring, quinoxaline ring, different Quinoline ring, carbazole ring, phenazin ring, acridine ring, phenanthroline ring, thioxan ring, benzopyran ring, xanthene ring, morphine ring, phenothiazine ring, and phenazine ring, most Good for benzene ring. The plurality of aromatic rings of the aryl group may be linked via a single bond or a linking group to be described later. As the linking group, for example, an alkyl group is preferred. The alkylene group is preferably a linear or branched form. Specific examples of the aryl group in which a plurality of aromatic rings are bonded via a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, and tetraphenyl. Methane and the like.

Examples of the substituent which the organic group represented by A ¹ may include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; or an alkyl group such as a methoxy group, an ethoxy group or a third butoxy group; An oxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an ethoxy group, a propenyloxy group and a benzamidine group; An oxiranyl group; an alkyl group such as an alkyl group, a benzamidine group, an isobutyl group, an acryl group, a methacryl group, and a methoxycyanyl group; an alkyl group such as a methyl group or a tert-butyl group; An aryl fluorenyl group such as a phenyl fluorenyl group and a p-tolyl fluorenyl group; a linear or branched alkyl group such as a methyl group, an ethyl group, a tert-butyl group or a dodecyl group; a halogenated alkyl group such as a fluorinated alkyl group; a cyclic alkyl group such as a cyclyl group, a cyclohexyl group, a cycloheptyl group or an adamantyl group; an aryl group such as a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthracenyl group or a phenanthryl group; a hydroxyl group; Mercapto; sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonylamino; decylalkyl; amine; monoalkylamine; dialkylamine ; Aryl group; diaryl group; sulfoxy; and combinations of the plurality.

L ¹ represents a (m+1)-valent linking group. The linking group is not particularly limited, and examples thereof include -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, and an alkylene group (preferably a carbon number). a linear alkyl group or a branched alkyl group of 1 to 10, a cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms), an alkenyl group (preferably a carbon having a carbon number of 2 to 10) a chain extending alkenyl group or a branched chain extending alkenyl group), and a plurality of linking groups formed by these. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkyl group, a cycloalkyl group, an alkenyl group group, more preferably a linear alkyl group or a branched alkyl group, and more preferably a linear alkyl group, particularly preferably an ethyl group or an alkyl group. Methyl, most preferably methylene.

R ¹ represents a monovalent organic group. Examples of the monovalent organic group include an aliphatic group, an aryl group and the like. Examples of the aliphatic group and the aryl group include those described in the above A ¹ . The monovalent organic group represented by R ¹ may have a substituent. R ^{1 is} preferably a group having a carboxyl group. That is, R ^{1 is} preferably a group represented by the formula. -L ² -(COOH) _{n In the} formula, L ² represents a (n+1)-valent linking group, and n represents an integer of 1 or more. The linking group represented by L ² may be the group described in the above L ¹ , and the preferred range is also the same, and particularly preferably an ethyl group or a methylene group, and most preferably a methylene group. n represents an integer of 1 or more, preferably 1 or 2, more preferably 1. The upper limit of n is the maximum number of substituents which can be used for the linking group represented by L ² . When n is 1, the tertiary amine having a high boiling point is easily generated by heating at or below the maximum heating temperature. Further, the stability of the composition can be improved.

m represents an integer of 1 or more, preferably 1 or 2, more preferably 1. The upper limit of m is the maximum number of substituents which can be used for the linking group represented by L ¹ . When m is 1, the tertiary amine having a high boiling point is easily generated by heating at or below the maximum heating temperature. Further, the stability of the composition can be improved. p represents an integer of 1 or more, preferably 1 or 2, more preferably 1. The upper limit of p is the maximum number of substituents which the organic group represented by A ¹ can employ. When p is 1, the tertiary amine having a high boiling point is easily generated by heating at or below the maximum heating temperature.

In the present invention, the compound represented by the formula (1A) is preferably a compound represented by the following formula (1a). General formula (1a) [化32] In the formula (1a), A ¹ represents a p-valent organic group, L ¹ represents a (m+1)-valent linking group, L ² represents a (n+1)-valent linking group, and m represents an integer of 1 or more, n An integer of 1 or more is represented, and p represents an integer of 1 or more. The meanings of A ¹ , L ¹ , L ² , m, n and p of the formula (1a) are the same as those described in the formula (1A), and the preferred ranges are also the same.

In the present invention, the compound represented by the formula (1A) is preferably N-aryliminodiacetic acid. The N-aryliminodiacetic acid is a compound in which the A ¹ in the formula (1A) is an aryl group, L ¹ and L ² are a methylene group, m is 1, n is 1, and p is 1. N-aryliminodiacetic acid easily produces a tertiary amine having a high boiling point at 120 ° C to 200 ° C.

Specific examples of the hot amine generating agent in the present invention are described below, but the present invention is not limited to these specific examples. These may be used alone or in combination of two or more. Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-11), (A-18), and (A-19) are the compounds represented by the above formula (1). Among the compounds shown below, (A-1) to (A-11), (A-18) to (A-26), and more preferably (A-1) to (A-9), (A-18) to (A-21), (A-23), and (A-24). Moreover, from the viewpoint of improving the adhesion to copper, it is preferably (A-18) to (A-26), (A-38) to (A-43), and more preferably (A-26). (A-38) to (A-43).

[Table 1]

[Table 2] [table 3] [Table 4] [table 5]

<<Photoamine generator>> The photoamine generator is suitable for the negative type because the base generated by the exposure acts as a catalyst when the polymer precursor containing the hetero ring is cured by heating. use.

In the present invention, as the photoamine generating agent, a known one can be used. For example, M. Shirai, and M. Tsunooka, Progress in Polymer Science, Prog. Polym. Sci., 21, 1 (1996) Kakuoka Masahiro, "Polymer Processing", 46, 2 (1997); C. Kutal, "Coordination Chemistry Reviews, Coord. Chem. Rev.", 211, 353 (2001); Y. Gold and A. Sarke, and D. Neckers, "Chemistry of Materials, Chem. Mater.", 11, 170 (1999); H .. and H. Tachi, M. Shirai, and M. Tsunooka, Journal of Photopolymer Science and Technology, J. Photopolym. Sci. Technol .)", 13, 153 (2000); M. Winkle, and Graziano, "J. Photopolym. Sci. Technol." 3, 419 (1990); M. Kakuoka and H. T. and M. Tsunooka, H. Tachi, and S. Yoshitaka, Journal of Photopolymer Science and Technology (J. Photopolym) Sci. Technol.)", 9, 13 (1996); K. Shoushan and H. Araki and M. Shirai, "Journal of Photopolymer Science and Technology (J) . Photopolym. Sci. Technol.)", 19, 81 (2006), which has a structure such as an ammonium salt or a salt formed by an amine such as a salt formed by a hydrazine moiety and a carboxylic acid. The neutralized ionic compound, or a urethane derivative, an oxime ester derivative, a mercapto compound or the like, is a nonionic compound which is latent by an alkali component such as a urethane bond or a hydrazone bond.

Examples of the amine produced from the photo-amine generating agent include a polyamine such as a monoamine or a diamine, or hydrazine. The amine produced is preferably a diamine or an aliphatic amine. The reason for this is that such an amine has a strong catalytic effect on ruthenium imidization of a heterocyclic-containing polymer precursor or a dehydration condensation reaction in oxazole, and is added in a smaller amount at a lower temperature. The catalyst effect in the dehydration condensation reaction or the like can be exhibited. That is, since the catalyst effect of the produced amine is large, the apparent sensitivity as a composition is improved. The amine in the present invention is, for example, a base generator having a guanyl cinnamate structure as disclosed in Japanese Laid-Open Patent Publication No. 2009-80452 and International Publication No. 2009/123122. An alkali-generating agent having a urethane structure as disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2008-247747, and Japanese Patent Laid-Open No. Hei. No. 2007-249013, and Japanese Patent Laid-Open No. 2008-003581 The amine having an anthracene structure or an amine formamidine structure as disclosed in the publication is not limited thereto, and a known amine structure may be used.

Hereinafter, the photoamine generating agent usable in the present invention will be described by way of specific examples. Examples of the ionic compound include those having the following structural formula.

[化33]

Examples of the mercapto compound include compounds represented by the following formulas.

[化34]

In addition, examples of the photoamine generating agent include compounds represented by the following formula (PB-1).

[化35] (PB-1)

(In the formula (PB-1), R ⁴¹ and R ⁴² are each independently a hydrogen atom or an organic group, and may be the same or different; wherein at least one of R ⁴¹ and R ⁴² is an organic group; or, regarding R ⁴¹ And R ⁴² , which may be bonded to form a ring structure, and may also contain a bond of a hetero atom; R ⁴³ and R ⁴⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol. a base, a nitro group, a nitroso group, a sulfinic acid group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonate group, or an organic group, which may be the same or different; R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a thiol group, a thioether group, a decyl group, a decyl alcohol group, a nitro group, a nitroso group, a sulfinic acid group, a sulfo group, a sulfonate group. , phosphino, phosphinyl, phosphinyl, phosphonate, amine, ammonium or organic, may be the same or different; or, with respect to R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ , More than one may be bonded to form a ring structure, and may also contain a bond of a hetero atom; R ⁴⁹ is a hydrogen atom or may be deprotected by irradiation with heat and/or electromagnetic waves Protection base)

Specific examples of the formula (PB-1) are listed below, but are not limited thereto.

[化36]

[化37]

[化38]

In addition, examples of the photoamine generating agent include the compounds described in Paragraph No. 0185 to Paragraph No. 0188, Paragraph No. 0199 to Paragraph No. 0200, and Paragraph No. 0202 of JP-A-2012-93746, Japanese Patent No. The compound described in paragraphs 0022 to 0069 of JP-A-2013-194205, the compound described in paragraph 0026 to paragraph 0074 of JP-A-2013-204019, and WO2010/064631 The compound described in Paragraph No. 0052 is taken as an example, and the contents are incorporated in the present specification.

When an amine generator is used, the content of the amine generator in the composition is preferably from 0.1% by mass to 50% by mass based on the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and still more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. Further, the amine generator is preferably contained in a ratio of 0.01% by mass to 45% by mass based on the total amount of the polyimide intermediate and the polybenzoxazole precursor. The lower limit of the total amount of the amine generator relative to the polyimide intermediate and the polybenzoxazole precursor is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1.0% by mass. the above. The upper limit is more preferably 35.0% by mass or less, still more preferably 28.0% by mass or less, still more preferably 12% by mass or less, and still more preferably 6.0% by mass or less. By setting it as the said range, the effect of this invention is exerted more effectively. In particular, when the amount of the amine generator is 6.0% by mass or less, the amine generator becomes less likely to remain in the cured film, and the outgassing component can be further reduced. In addition, by setting the amount of the amine generator to 0.2% by mass or more, the hardening can be further promoted, and the outgassing component can be reduced. The amine generator may be used alone or in combination of two or more. When two or more types are used, it is preferred that the total amount is the above range.

The composition used in the present invention may be used in addition to the amine generating agent, or may be used without using other thermal base generators. The composition in the present invention may be configured to be substantially free of other thermal base generating agents. The term "substantially free" means, for example, 0.1% by mass or less based on the amount of the amine generator contained in the composition.

The composition used in the present invention is preferably an amine having a pKa8 or more which does not contain a conjugate acid. Here, the composition does not contain an amine having a pKa8 or more of a conjugate acid, and the main purpose is to contain substantially no pKa8 or more amine of the conjugate acid in the composition. In the range of 0.001% by mass or less of the amine generator contained in the composition or the detection limit or less, it is of course not included in the range which does not deviate from the scope of the present invention. . As described above, since the composition before the start of the cyclization reaction of the heterocyclic-containing polymer precursor does not contain an amine having a pKa8 or more of a conjugate acid, the amount of the amine of the cured film can be more easily adjusted. Further, the composition of the present invention preferably contains substantially no amine before heating. In the case where the content of the amine generating agent contained in the composition is 0.001% by mass or less, it is of course not substantially excluded.

<Other components contained in the composition> When the composition used in the present invention contains a polymer precursor containing a hetero ring and an amine generator, the other components are not particularly limited, and other components may be appropriately formulated depending on the use and the like. The composition used in the present invention is particularly preferably a photosensitive resin composition, but is not necessarily limited to those having photosensitivity. The first embodiment of the photosensitive resin composition of the present invention comprises a heterocyclic-containing polymer precursor and a photoradical polymerization initiator. Such a photosensitive resin composition can be preferably used as a negative photosensitive resin composition. When used as a negative photosensitive resin composition, it is preferred that the heterocyclic-containing polymer precursor has a polymerizable unsaturated group or a crosslinking agent. When the photosensitive resin composition is a negative photosensitive resin composition, the crosslinking agent preferably contains a compound having an ethylenically unsaturated bond. The second embodiment of the photosensitive resin composition of the present invention comprises a heterocyclic-containing polymer precursor and a photoacid generator. Such a photosensitive resin composition can be preferably used as a positive photosensitive resin composition. When used as a positive photosensitive resin composition, it is preferable to contain a curable composition. When the photosensitive resin composition is a positive photosensitive resin composition, the crosslinking agent is preferably selected from a compound having a hydroxymethyl group, an alkoxymethyl group or a decyloxymethyl group, an epoxy compound, and oxygen. At least one compound of a heterocyclic butane compound and a benzoxazine compound. Further, the negative photosensitive resin composition may contain a sensitizer, a polymerization inhibitor, or the like. In addition, it is of course possible to include components other than these. On the other hand, the positive photosensitive resin composition may also contain a resin having a phenolic OH group. In addition, it is of course possible to include components other than these. Details of these ingredients will be described later. In particular, when it is a positive photosensitive resin composition, it is preferable that the polymer precursor containing a hetero ring contains a polybenzoxazole precursor. Further, the composition used in the present invention may also contain a polycyclic imine or a polybenzoxazole or the like having a closed-loop structure.

The content of the heterocyclic-containing polymer precursor in the composition used in the present invention is preferably 20% by mass to 100% by mass, and more preferably 50% by mass to 99% by mass, based on the total solid content of the composition. Further, it is more preferably 70% by mass to 98% by mass, particularly preferably 80% by mass to 95% by mass. Hereinafter, components which can be contained in the composition used in the present invention will be described. Of course, the invention may also contain ingredients other than those which are not necessary.

<Crosslinking Agent> The composition used in the present invention may contain a crosslinking agent as a preferred embodiment. By including a crosslinking agent, the cyclization reaction of the heterocyclic-containing polymer precursor at a low temperature can be more efficiently carried out. Further, by containing a crosslinking agent, a cured film having more excellent heat resistance can be formed. In addition, pattern formation using photolithography can also be performed. When the compounding is carried out, the content of the crosslinking agent is preferably from 1% by mass to 40% by mass, and more preferably from 10% by mass to 30% by mass based on the total amount of the heterocyclic polymer precursor in the composition. The crosslinking agent may be used singly or in combination of two or more. When two or more kinds of crosslinking agents are used, it is preferred that the total amount is in the above range.

The crosslinking agent is a compound having a crosslinkable group, and a known compound which can be subjected to a crosslinking reaction by a radical, an acid, an alkali or the like can be used. The crosslinkable group is a group which can be subjected to a crosslinking reaction by the action of actinic rays, radiation, a radical, an acid or a base, and a preferred example thereof is a group having an ethylenically unsaturated bond. Hydroxymethyl, decyloxymethyl, alkoxymethyl, epoxy, oxetanyl, benzoxazolyl. The compound having an ethylenically unsaturated bond used in the present invention is more preferably a compound containing two or more ethylenically unsaturated groups, and still more preferably a compound containing two to six ethylenically unsaturated groups. It is a compound containing 2 to 4 ethylenically unsaturated groups. The crosslinking agent may be, for example, any of a chemical form such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a polymer of the above. The compound having an ethylenically unsaturated bond is preferably a monomer.

In the present invention, the monomer type crosslinking agent (hereinafter also referred to as a crosslinkable monomer) is a compound different from the polymer compound. The crosslinkable monomer is typically a low molecular compound, preferably a low molecular weight compound having a molecular weight of 2,000 or less, more preferably a low molecular weight compound having a molecular weight of 1,500 or less, and still more preferably a low molecular weight compound having a molecular weight of 900 or less. Further, the molecular weight of the crosslinkable monomer is usually 100 or more. Further, the oligomer-type crosslinking agent is typically a polymer having a relatively low molecular weight, and preferably a polymer in which 10 to 100 crosslinkable monomers are bonded. The molecular weight, the weight average molecular weight is preferably from 2,000 to 20,000, more preferably from 2,000 to 15,000, most preferably from 2,000 to 10,000.

In the present invention, the number of functional groups of the crosslinking agent means the number of crosslinking groups in one molecule. From the viewpoint of analytical properties, the crosslinking agent preferably contains at least one crosslinking agent having two or more crosslinking groups, and more preferably contains at least one crosslinking agent having at least one trifunctional or higher functional group. The upper limit of the crosslinkable group is not particularly limited, and is, for example, 8 or less, preferably 6 or less. The crosslinkable group is preferably a radical polymerizable group. In other words, as the crosslinking agent in the present invention, a compound having two or more radical polymerizable groups can be exemplified. In the present invention, it is particularly preferred that the polymer precursor containing a hetero ring has a radical polymerizable group and a crosslinking agent having a radical polymerizable group. Further, in terms of forming a three-dimensional crosslinked structure to improve heat resistance, the crosslinking agent in the present invention preferably contains at least one trifunctional or higher crosslinking agent. Further, it may be a mixture of a difunctional or lower crosslinking agent and a trifunctional or higher crosslinking agent.

<<Compound having an ethylenically unsaturated bond>> As a group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth)acryl fluorenyl group, and a (meth)allyl group are preferable. It is a (meth) acrylonitrile group.

Specific examples of the compound having an ethylenically unsaturated bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof. The guanamines and the multimers thereof are preferably esters of an unsaturated carboxylic acid and a polyol compound, and guanamines of an unsaturated carboxylic acid and a polyamine compound, and a multimer of these. Further, an ester or an oxime of an unsaturated carboxylic acid having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition reaction product with a monofunctional or polyfunctional isocyanate or an epoxy group may be suitably used. Or a dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid or the like. Further, an ester of an unsaturated carboxylic acid having an electrophilic substituent such as an isocyanate group or an epoxy group, or an addition reaction product of a monofunctional or polyfunctional alcohol, an amine or a thiol, A substituted reactant of an unsaturated carboxylic acid having a detachable substituent such as a halogen group or a tosyloxy group or a guanamine and a monofunctional or polyfunctional alcohol, an amine or a thiol is also suitable. Further, as another example, a group of compounds substituted with a vinylbenzene derivative such as unsaturated phosphonic acid or styrene, vinyl ether or allyl ether may be used instead of the unsaturated carboxylic acid.

Specific examples of the monomer of the ester of the polyol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and the like as the acrylate. Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris(propylene oxypropyl) ether, trishydroxyl Ethylene triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, Dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tris(propylene methoxyethyl) iso-tri Polycyanate, iso-cyanuric acid ethylene oxide modified triacrylate, polyester acrylate oligomer, and the like.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and trimethylolpropane trimethacrylate. Trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, Pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, double [ (3-Methylpropenyloxy-2-hydroxypropoxy)phenyl]dimethylmethane, bis-[p-(methacryloxyethoxy)phenyl]dimethylmethane, and the like.

As itaconate, there are ethylene glycol diitaric acid ester, propylene glycol II itaconate, 1,3-butylene glycol isaconate, 1,4-butanediol diitaric acid ester, and four Methylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraconate, and the like.

Examples of the crotonate include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetra-dicrotonate.

Examples of the isocrotonate include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

As the maleic acid ester, there are ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleic acid. Ester and the like.

As an example of the other ester, for example, an aliphatic alcohol ester described in Japanese Patent Publication No. Sho 46-27926, Japanese Patent Publication No. Sho 51-47334, and Japanese Patent Laid-Open Publication No. SHO 57-196231 A compound having an aromatic skeleton described in Japanese Patent Laid-Open No. Hei 59-5241, Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. A compound containing an amine group described in JP-A-165613.

Further, specific examples of the monomer of the polyamine compound and the decylamine of the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methyl acrylamide, and 1,6-hexamethylene group. Bis-acrylamide, 1,6-hexamethylenebis-methylpropenylamine, diethylenetriaminetripropenylamine, xylylenebisacrylamide, xylylene bismethacrylamide, and the like.

As an example of another preferable amide-based monomer, a monomer having a cyclohexylene structure described in Japanese Patent Publication No. Sho 54-21726 can be cited.

In addition, a urethane-based addition polymerizable monomer produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable, and as such a specific example, for example, it is described in JP-A-48-41708. In a polyisocyanate compound having two or more isocyanate groups in one molecule, a vinyl group containing a hydroxyl group represented by the following formula is added to contain one or more polymerizable vinyl groups in one molecule. A vinyl urethane compound or the like. CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH (wherein R ⁴ and R ⁵ represent H or CH ₃ ) Further, as disclosed in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Special Publication No. 2 Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 58-49860, Japanese Patent Publication No. SHO 56-17654, and Japanese Patent Publication No. Sho 62-62 A urethane compound having an ethylene oxide skeleton described in Japanese Patent Publication No. Sho 62-39418 is also suitable.

Further, in the present invention, as the compound having an ethylenically unsaturated bond, the compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can also be suitably used.

Further, as the compound having an ethylenically unsaturated bond, a compound having a boiling point of 100 ° C or higher at normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and phenoxyethyl (meth)acrylate. Polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol IV (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (meth) acrylate, trimethylolpropane tri (propylene oxypropyl propyl) (meth)acrylic acid after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol, such as ether, tris(propylene methoxyethyl) isomeric cyanurate, glycerin or trimethylolethane The esterification of the (meth)acrylic acid urethanes as described in the Japanese Patent Publication No. Sho-48-41708, the Japanese Patent Publication No. Sho. Japanese Patent Publication No. Sho 48-64183, Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho 52-30490 Polyester acrylates described in JP, as a reaction product of an epoxy resin and (meth) acrylic acid esters of polyfunctional epoxy acrylates acrylates and methacrylates, and mixtures of the plurality. Further, the compound described in Paragraph No. 0254 to Paragraph No. 0257 of JP-A-2008-292970 is also suitable. In addition, a polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group or an ethylenically unsaturated group such as glycidyl (meth)acrylate may be used. In addition, as another preferable compound having an ethylenic unsaturated bond, those described in JP-A-2010-160418, JP-A-2010-129825, and JP-A No. 4364216, etc., may be used. A compound having an anthracene ring and having two or more groups containing an ethylenically unsaturated bond, or a cardo resin. Further, as another example, a specific unsaturated compound described in Japanese Patent Publication No. Sho 46-43946, Japanese Patent Publication No. Hei. No. Hei. A vinylphosphonic acid-based compound or the like described in JP-A No. 2-25493. In addition, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is suitably used. Further, it is also possible to use as a photocrosslinkable monomer and oligomer in "Japan Next Association" Vol. 20, No. 7, 300 pages to 308 (1984).

In addition to the above, a compound having an ethylenically unsaturated bond represented by the following formula (MO-1) to formula (MO-5) can be suitably used. Further, in the formula, when T is an alkyloxy group, the terminal on the carbon atom side is bonded to R.

[39]

[化40]

In the formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. R and T in a single molecule may be the same or different. In each of the polymerizable compounds represented by the general formula (MO-1) to the general formula (MO-5), at least one of the plurality of R represents -OC(=O)CH=CH ₂ , or -OC(=O)C(CH ₃ )=the group represented by CH ₂ . In the present invention, as a specific example of the compound having an ethylenically unsaturated bond represented by the above formula (MO-1) to (MO-5), Japanese Patent Laid-Open No. 2007- The compound described in Paragraph No. 0248 to Paragraph No. 0251 of 269779.

The following compounds which are described in the general formula (1) and the general formula (2) together with the specific examples thereof can also be used as a polymerizable compound in a polyfunctional alcohol, as disclosed in Japanese Laid-Open Patent Publication No. Hei 10-62986. A compound obtained by (meth)acrylation after addition of ethylene oxide or propylene oxide.

As the compound having an ethylenically unsaturated bond, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (preferably) The products sold are KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; Nippon Kayak) Pharmaceutical Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and these (meth) acrylonitrile groups A structure bonded via an ethylene glycol residue or a propylene glycol residue. These oligomer types can also be used.

The compound having an ethylenically unsaturated bond may also be a polyfunctional monomer having an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, more preferably an acid group having an unreacted hydroxyl group of the aliphatic polyhydroxy compound reacted with a non-aromatic carboxylic anhydride. The polyfunctional monomer, particularly preferably in the ester, is an aliphatic polyhydroxy compound which is pentaerythritol and/or dipentaerythritol. As a commercial item, M-510, M-520, etc. which are polyacid-acid-modified acrylic oligomer manufactured by the East Asia Synthetic Co., Ltd. are mentioned, for example. The polyfunctional monomer having an acid group may be used singly or in combination of two or more. Further, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as needed. The preferred acid value of the polyfunctional monomer having an acid group is from 0.1 mgKOH/g to 40 mgKOH/g, particularly preferably from 5 mgKOH/g to 30 mgKOH/g. When the acid value of the polyfunctional monomer is in the above range, the production or handling property is excellent, and further, the developability is excellent. In addition, the crosslinkability is good.

As the compound having an ethylenically unsaturated bond, a compound having a caprolactone structure can also be used. The compound having a caprolactone structure and an ethylenically unsaturated bond is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trishydroxymethylethane and di-trimethylol B. Polyols such as alkane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, trimethylol melamine, and (meth)acrylic acid and ε-caprolactone The ε-caprolactone obtained by esterification is modified with a polyfunctional (meth) acrylate. Among them, a polymerizable compound having a caprolactone structure represented by the following formula (C) is preferred.

General formula (C) [41]

(In the formula, all of the six R's are represented by the following formula (D), or one to five of the six R's are represented by the following formula (D), and the remainder is a group represented by the following general formula (E)

General formula (D) [Chem. 42]

(wherein R ¹ represents a hydrogen atom or a methyl group, m represents 1 or 2, and "*" represents a bond)

General formula (E) [化43]

(wherein R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond)

Such a polymerizable compound having a caprolactone structure is commercially available, for example, as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and may be exemplified by DPCA-20 (the above formula (C) to the formula In (E), m = 1, a compound represented by the formula (D) = 2, a compound in which R ¹ is a hydrogen atom), DPCA-30 (the above formula (C) to a formula (E) In the formula (C) to (E), m = 1, a compound represented by the formula (D) = 3, a compound in which R ¹ is a hydrogen atom), and DPCA-60 (in the formula (C) to (E) , m = 1, a compound represented by the formula (D) = 6 and a compound in which R ¹ is a hydrogen atom), DPCA-120 (in the above formula (C) to (E), m = 2, the number of the groups represented by the formula (D) = 6, the compound in which R ¹ is a hydrogen atom) and the like. In the present invention, the compound having a caprolactone structure and an ethylenically unsaturated bond may be used singly or in combination of two or more.

The compound having an ethylenically unsaturated bond is preferably at least one selected from the group consisting of compounds represented by the following formula (i) or formula (ii).

[化44]

In the general formula (i) and the general formula (ii), E independently represents -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ )O)-, y respectively Independently, an integer of 0 to 10 is represented, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group. In the general formula (i), the total of (meth)acrylonyl groups is three or four, and m each independently represents an integer of from 0 to 10, and the total of each m is an integer of from 0 to 40. However, when the total of each m is 0, any one of X is a carboxyl group. In the general formula (ii), the total of (meth)acrylonyl groups is 5 or 6, and n each independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60. However, when the total of each n is 0, any one of X is a carboxyl group.

In the formula (i), m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8. In the formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the total of each n is preferably an integer of from 3 to 60, more preferably an integer of from 3 to 24, and particularly preferably an integer of from 6 to 12. -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ )O)- in the formula (i) or the formula (ii) is preferably a terminal bond on the oxygen atom side Formed on X. In particular, it is preferred that in the general formula (ii), six Xs are in the form of an acrylonitrile group.

The compound represented by the general formula (i) or the general formula (ii) can be synthesized by the following steps as a previously known step: ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide The step of bonding the ring-opening skeleton and the step of introducing a (meth)acrylonitrile group by reacting, for example, (meth)acrylofluorene chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person represented by the formula (i) or the formula (ii) can be easily synthesized by a person skilled in the art.

Among the compounds represented by the general formula (i) and the general formula (ii), a pentaerythritol derivative and a dipentaerythritol derivative are more preferable. Specifically, a compound represented by the following formula (a) to formula (f) (hereinafter also referred to as "exemplary compound (a) to exemplary compound (f)")), preferably an exemplified compound (a), exemplified compound (b), exemplified compound (e), and exemplified compound (f).

[化45]

[Chem. 46]

As a commercial item of the polymerizable compound represented by the general formula (i) and the general formula (ii), for example, a tetrafunctional acrylic acid having four ethylene ethoxylate chains manufactured by Sartomer Co., Ltd. is mentioned. Ester SR-494, DPCA-60 manufactured by Nippon Kayaku Co., Ltd. as a hexafunctional acrylate having 6 pentyloxy chains, and TPA as a trifunctional acrylate having 3 extended isobutoxy chains -330 and so on.

As a compound having an ethylenic unsaturated bond, for example, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Laid-Open No. Sho 51-37193, Japanese Patent Laid-Open No. 2-32293, Japanese Patent Publication No. Hei 2-16765 The urethane amides described in Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. SHO 62-39418 A urethane compound having an ethylene oxide skeleton described in the publication is also suitable. Further, as the polymerizable compound, an amine group having a molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-10-15238 can be used. An addition polymerizable monomer of a structure or a thioether structure. Commercial products of the compound having an ethylenically unsaturated bond include urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku Pulp Co., Ltd.), and NK ESTER (NK ESTER). ) M-40G, NK Ester 4G, NK ESTER M-9300, NK ESTER A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Made in Japan), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (Day Oil (shares) manufacturing, etc.

From the viewpoint of heat resistance, the compound having an ethylenically unsaturated bond preferably has a partial structure represented by the following formula. Where * in the formula is a link key.

[化47]

Specific examples of the compound having an ethylenically unsaturated bond having the partial structure include, for example, trimethylolpropane tri(meth)acrylate and isomeric cyanuric acid ethylene oxide modified di(methyl). Acrylate, iso-cyanuric acid ethylene oxide modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(methyl) ) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra (meth) acrylate, etc., which are particularly preferably used in the present invention Compound. Further, a compound having n of 3 to 25 in the following composition may be mentioned as a preferred example. [48]

In the composition, the content of the compound having an ethylenically unsaturated bond is preferably from 1% by mass to 50% by mass based on the total solid content of the composition from the viewpoint of good crosslinkability and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 25% by mass or less. The compound having an ethylenically unsaturated bond may be used singly or in combination of two or more. Further, the mass ratio of the heterocyclic-containing polymer precursor to the compound having an ethylenically unsaturated bond (the heterocyclic-containing polymer precursor/polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and further preferably 90/10 to 50/50, and more preferably 90/10 to 70/30. When the mass ratio of the polymer precursor containing a hetero ring and the compound having an ethylenically unsaturated bond is in the above range, a cured film having more excellent crosslinkability and heat resistance can be formed. The compound having an ethylenically unsaturated bond may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Compound having a hydroxymethyl group, an alkoxymethyl group or a decyloxymethyl group> As the compound having a hydroxymethyl group, an alkoxymethyl group or a decyloxymethyl group, it is preferred to have the following formula (AM1) ) the compound represented.

[化49] (AM1) (wherein t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, and R ⁵ represents a general formula (AM2) or a formula (AM3) Base of representation)

[化50] (AM2) (AM3) (wherein R ⁶ represents a hydroxyl group or an organic group having 1 to 10 carbon atoms)

The content of the compound represented by the formula (AM1) is preferably 5 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the polymer precursor containing a hetero ring. More preferably, it is 10 mass parts or more and 35 mass parts or less. In addition, it is preferable that the compound represented by the following formula (AM4) is contained in an amount of 10% by mass or more and 90% by mass or less, and all of the crosslinking agents are contained in an amount of 10% by mass or more. 90% by mass or less of a compound represented by the following formula (AM5). These compounds may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

[化51] (AM4) (wherein R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, and R ⁵ represents a group represented by the following formula (AM2) or the following formula (AM3))

[化52] (AM5) (wherein, u represents an integer of 3 to 8, and R ⁴ represents a u-valent organic group having a carbon number of 1 to 200, and R ⁵ represents a general formula (AM2) or the following general formula (AM3) Base of representation)

[化53] (AM2) (AM3) (wherein R ⁶ represents a hydroxyl group or an organic group having 1 to 10 carbon atoms)

Among the above, the following compounds can be exemplified as the compound having two or more hydroxymethyl groups. [54] (In the chemical formula (1), R ^a is an organic group having 2 to 20 carbon atoms, and P ¹ is a hydrogen atom or an alkyl group.) R ^{a is} preferably a hydrocarbon group. P ^{1 is} preferably a hydrogen atom. For details of these, refer to the description of Paragraph No. 0010 to Paragraph No. 0024 of International Publication WO2010/038742, the contents of which are hereby incorporated herein.

By using the compound, when a composition layer is formed on a substrate having irregularities, the occurrence of cracks becomes less. Further, the pattern processability is excellent, and the heat resistance of 5% by mass is preferably 350 ° C or higher, more preferably 380 ° C or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (the above is a trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML. -PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above trade name, Honshu Chemical Industry Co., Ltd.) Manufactured), NIKALAC MX-290 (above trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6- Dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-p-cresol, and the like.

Further, specific examples of the compound represented by the general formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, and the like. HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), Nicarak (NIKALAC) MX-280, NIKALAC MX-270, NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).

Further, as the compound having a hydroxymethyl group, an alkoxymethyl group or a decyloxymethyl group, the following compounds are also preferred. T2058 and B1525 (above, the product name, manufactured by Tokyo Chemical Industry Co., Ltd.) can be exemplified as a commercial product. [化55]

<Epoxy compound (compound having an epoxy group)> As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferable. The epoxy compound undergoes a crosslinking reaction at 200 ° C or lower, and does not cause a dehydration reaction in the crosslinking reaction, so that it is difficult to cause film shrinkage. Therefore, it is effective to contain an epoxy compound for low-temperature hardening and low warpage of the composition.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus can be further reduced, and the low warpage can be further achieved. Further, a cured film which is excellent in flexibility and high in elongation and the like can be obtained. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and preferably the number of repeating units is 2 to 15.

Examples of the epoxy compound include a bisphenol A type epoxy resin; a bisphenol F type epoxy resin; an alkanediol type epoxy resin such as propylene glycol diglycidyl ether; and a polypropylene glycol diglycidyl ether. An alkanediol type epoxy resin; an epoxy group-containing anthrone or the like such as polymethyl (glycidoxypropyl) decane, but is not limited to these examples. Specifically, Epiclon (registered trademark) 850-S, Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Ai Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) EXA-4710, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-859CRP, Epiclon (registered trademark) EXA-1514, Epiclon (registered trademark) EXA-4880, Abby clone (Epiclon) (registered trademark) EXA-4850-150, Epiclon (registered trademark) EXA-4850-1000, Epiclon (registered trademark) EXA-4816, Epiclon (Epiclon) Registered trademark) EXA-4822 (above is the trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Physicochemical Resin (registered trademark) BEO-60E (above, trade name, New Japan Physical and Chemical Co., Ltd.), EP-4003S, EP-4000S (above is the trade name, ADEKA (shares) and so on. Among them, in terms of low warpage and excellent heat resistance, an epoxy resin containing a polyethylene oxide group is preferred. For example, Epiclon (registered trademark) EXA-4880, Epiclon (registered trademark) EXA-4822, and physicochemical resin (registered trademark) BEO-60E are preferred because they contain a polyethylene oxide group. .

The content of the epoxy compound is preferably from 5 parts by mass to 50 parts by mass, more preferably from 10 parts by mass to 50 parts by mass, even more preferably from 10 parts by mass to 40 parts by mass per 100 parts by mass of the polymer precursor containing a hetero ring. Parts by mass. When the amount is 5 parts by mass or more, the warpage of the cured film can be further suppressed. When the amount is 50 parts by mass or less, pattern burying accompanying the reflow at the time of final heating (curing) can be further suppressed. The epoxy compound may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Oxetane compound (compound having oxetanyl group)> Examples of the oxetane compound include a compound having two or more oxetane rings in one molecule, and 3-ethyl group. 3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-( 2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, and the like. As a specific example, a series of arylene oxetane (for example, OXT-121, OXT-221, OXT-191, and OXT-223) manufactured by Toagosei Co., Ltd. may be suitably used, and these may be used alone or may be used alone. Mix two or more.

The content of the oxetane compound is preferably from 5 parts by mass to 50 parts by mass, more preferably from 10 parts by mass to 50 parts by mass, even more preferably 10% by mass based on 100 parts by mass of the polymer precursor containing a hetero ring. Parts - 40 parts by mass. The oxetane compound may be used singly or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Benzothoxazine compound (compound having benzoxazolyl group)> The benzoxazine compound generates a crosslinking reaction by a ring-opening addition reaction, so that degassing due to solidification does not occur, and The shrinkage caused by heat is small. Therefore, the occurrence of warpage can be suppressed.

Preferable examples of the benzoxazine compound include Ba-type benzoxazine, Bm-type benzoxazine (above, trade name, manufactured by Shikoku Chemical Industries, Ltd.), and benzoxazole of polyhydroxystyrene resin. Azine adduct, phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

The content of the benzoxazine compound is preferably from 5 parts by mass to 50 parts by mass, more preferably from 10 parts by mass to 50 parts by mass, even more preferably 10 parts by mass, based on 100 parts by mass of the polymer precursor containing a hetero ring. ~40 parts by mass. The benzoxazine compound may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

The crosslinking agent used in the present invention preferably has a molecular weight of from 100 to 1,500, more preferably from 100 to 800, still more preferably from 100 to 600. By setting the molecular weight to 800 or less and further to 600 or less, the outgassing property can be more effectively improved.

<Resin having a phenolic OH group> When the composition in the present invention is an alkali-developable positive photosensitive resin composition, in terms of adjusting the solubility to an alkaline developer and obtaining a good sensitivity, It is preferred to contain a resin having a phenolic OH group. As a resin which has a phenolic OH group, a novolak resin and a polyhydroxy styrene resin are mentioned as a preferable example.

<<Novolak Resin>> The novolac resin is obtained by polycondensing a phenol and an aldehyde by a well-known method. The novolac resin may be combined in combination of two or more. Preferable examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, and 3,4-xylenol. , 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, and the like. Particularly preferred are phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol and 2,3,5 - Trimethylphenol. These phenols may be used in combination of two or more kinds. From the viewpoint of the solubility of the alkaline developer, m-cresol and a combination of m-cresol and p-cresol are preferred. That is, as the novolac resin, a cresol novolak resin containing a m-cresol residue or a m-cresol residue and a p-cresol residue is preferable. At this time, the molar ratio (m-cresol residue/p-cresol residue, m/p) of the m-cresol residue to the p-cresol residue in the cresol novolak resin is preferably 1.8 or more. If it is this range, the moderate solubility with respect to an alkaline developing solution is shown, and the favorable sensitivity is acquired. More preferably 4 or more. Further, preferred examples of the aldehydes include formalin, polyoxymethylene, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, and chloroacetaldehyde. It is also possible to use two or more of these aldehydes.

In addition, in terms of imparting high heat resistance to the cured film of the composition of the present invention, the following wholly aromatic novolak resin is preferably used as the phenol by the following formula (Phe). The compound represented by the following formula (Ald) as an aldehyde is obtained by polycondensation using an acidic catalyst.

General formula (Phe) [化56] In the formula (Phe), R ₁ represents an organic group selected from an alkyl group and an alkoxy group having 1 or more carbon atoms and 20 or less carbon atoms, and p is an integer of 1 or more and 3 or less, preferably 2 or more and 3 or less. Integer.

General formula (Ald) [化57] In the general formula (Ald), R ₂ represents a group selected from the group consisting of hydrogen, an alkyl group having 1 or more and 20 or less carbon atoms, an alkoxy group and a hydroxyl group, and q represents an integer of 0 or more and 3 or less.

The phenol compound represented by the above formula (Phe) is a phenol compound having a number of substituents of 1 or more and 3 or less, preferably 2 or more and 3 or less, and the substituent is selected from a carbon number. It is an organic group in the alkyl group and alkoxy group of 1 or more and 20 or less. In addition, examples of the alkyl group and the alkoxy group having 1 or more and 20 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group, and an ethoxy group. As such a phenol compound, for example, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol can be preferably used. , 3,4-dimethylphenol, 3,5-dimethylphenol, 2-methyl-3-ethyl-phenol, 2-methyl-3-methoxyphenol, 2,3,4-tri Methyl phenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, and the like. Among these, it is not particularly limited, but is preferably selected from the group consisting of 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, and 3,4-dimethylphenol. Among 3,5-dimethylphenol and 2,6-dimethylphenol. Further, these phenols may be used alone or in combination of two or more. By using the phenol compound having 1 or more and 3 or less, preferably 2 or more and 3 or less as the phenol compound, it is possible to suppress the intramolecular rotation and have sufficient heat resistance required for the composition. Phenolic resin.

The aromatic aldehyde compound represented by the above formula (Ald) is an aromatic aldehyde compound having an unsubstituted or substituted number of 3 or less, and the substituent is selected from a carbon number of 1 or more. An alkyl group, an alkoxy group or an organic group in a hydroxyl group of 20 or less. In addition, examples of the alkyl group and the alkoxy group having 1 or more and 20 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a methoxy group, and an ethoxy group. As such an aromatic aldehyde compound, for example, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 2,3-dimethylbenzaldehyde, 2,4- can be used. Dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, 2,3, 4-trimethylbenzaldehyde, 2,3,5-trimethylbenzaldehyde, 2,3,6-trimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde, 2,4,6- Trimethylbenzaldehyde, 3,4,5-trimethylbenzaldehyde, 4-ethylbenzaldehyde, 4-t-butylbenzaldehyde, 4-isobutylbenzaldehyde, 4-methoxybenzaldehyde, Salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 3-methylsauraldehyde, 4-methylsauraldehyde, 2-hydroxy-5-methoxybenzaldehyde, 2,4-dihydroxyl But benzaldehyde, 2,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, etc., but not limited thereto, and in these, R ₂ in the formula (2) is preferably hydrogen The aromatic aldehyde compound having a methyl group or a hydroxyl group is more preferably selected from the aromatic aldehyde compounds shown below. Further, these aldehydes may be used alone or in combination of two or more.

[化58]

In the synthesis reaction of obtaining a novolac resin from a phenol and an aldehyde, it is preferred to react the aldehyde compound at 0.5 mol or more and 2 mol or less with respect to the phenol compound 1 mol, more preferably 0.6 mol or more. The reaction of 1.2 m or less is particularly preferably a reaction of 0.7 mol or more and 1.0 mol or less. By setting the molar ratio, it is possible to obtain a molecular weight which can exhibit sufficient characteristics as a composition.

In the polycondensation reaction of phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and p-toluenesulfonic acid. The acid catalyst is usually used in an amount of from 1 × 10 ^-5 mol to 5 × 10 ^-1 mol per phenol. In the polycondensation reaction, water is usually used as the reaction medium, but when it is a non-uniform system from the initial stage of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium. Examples of the hydrophilic solvent include alcohols such as methanol, ethanol, propanol, butanol, and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane. Examples of the lipophilic solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The reaction medium is usually used in an amount of from 20 parts by mass to 1,000 parts by mass based on 100 parts by mass of the reaction raw material.

The reaction temperature of the polycondensation can be appropriately adjusted depending on the reactivity of the raw material, and is usually from 10 ° C to 200 ° C. As a reaction method of the polycondensation, a method in which a phenol, an aldehyde, an acid catalyst, or the like is simultaneously introduced and reacted may be suitably employed; or a phenol may be added in the presence of an acidic catalyst accompanying the progress of the reaction. Methods such as aldehydes and the like. After the completion of the polycondensation reaction, in order to remove the unreacted raw materials, the acidic catalyst, the reaction medium, and the like existing in the system, the reaction temperature is generally raised to 130 ° C to 230 ° C, and the volatile components are removed under reduced pressure and recovered. Novolak resin.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the novolak resin is preferably 1,000 or more, and more preferably 2,000 or more. Further, it is preferably 5,000 or less. If it is this range, good sensitivity can be obtained.

The content of the novolak resin is preferably 1 part by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the polymer precursor containing a hetero ring. If it is this range, the pattern which is high sensitivity and does not flow after heat processing at high temperature can be obtained. The novolak resin may be used singly or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<<Polyhydroxystyrene resin>> The hydroxystyrene resin is a polymer containing hydroxystyrene and/or a derivative thereof, and is not particularly limited, and may contain hydroxystyrene and/or a derivative thereof, and these A copolymer of a monomer other than the monomer. Examples of the monomer used herein include ethylene, propylene, 1-butene, 2-methylpropene, styrene, and derivatives thereof. Among them, a copolymer containing hydroxystyrene and/or a derivative thereof and styrene and/or a derivative thereof is preferred from the viewpoint of easily adjusting the solubility in an aqueous alkaline solution. The derivative is substituted with an ortho, meta, or para-alkyl group, an alkoxy group, a hydroxyl group or the like in the aromatic ring of hydroxystyrene and styrene. The hydroxystyrene of the hydroxystyrene resin may be any of o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene. Further, the hydroxystyrene may be mixed in a plurality of types.

The composition ratio of the hydroxystyrene and its derivative in the hydroxystyrene resin is preferably 50% or more, more preferably 60% or more. The upper limit is preferably 90% or less, more preferably 80% or less. By setting it as the said range, it is excellent in the coexistence of the fall of the residue after exposure of an exposure part, and the high sensitivity.

Among them, a hydroxystyrene resin having a repeating structural unit represented by the following formula (PHS-1) is preferred.

General formula (PHS-1) [化59] In the formula (PHS-1), R ₁ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, a represents 1 to 4, b represents 1 to 3, and a + b is in the range of 1 to 5. R ₂ represents an atom or a group selected from a hydrogen atom, a methyl group, an ethyl group or a propyl group.

The structural unit represented by the above formula (PHS-1) can be obtained, for example, by subjecting an alkoxy group to a partial reaction of a polymer or a copolymer obtained by a known method, the polymer or copolymerization An aromatic vinyl compound having a phenolic hydroxyl group such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol or o-isopropenylphenol by a known method. And obtained by polymerizing one or two or more kinds of aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. As the aromatic vinyl compound having a phenolic hydroxyl group, p-hydroxystyrene and/or m-hydroxystyrene can be preferably used, and an aromatic vinyl compound can preferably use styrene.

In the hydroxystyrene resin having a repeating structural unit represented by the above formula (PHS-1), it is preferred that the sensitivity is further improved and the solubility in the alkaline developing solution can be adjusted. A copolymer comprising a structural unit represented by the formula (PHS-2), the formula (PHS-3), and the formula (PHS-4). Further, in terms of solubility in an alkaline developer, the structural unit of the formula (PHS-4) is preferably 50 mol% or less.

General formula (PHS-2) [60] In the formula (PHS-2), R ₄ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, c represents 1 to 4, d represents 1 to 3, and c + d is in the range of 2 to 5. R ₃ represents an atom or a group selected from a hydrogen atom, a methyl group, an ethyl group or a propyl group.

General formula (PHS-3) [Chem. 61] In the formula (PHS-3), R ₅ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and e represents 1 to 5.

General formula (PHS-4) [Chem. 62] In the formula (PHS-4), R ₆ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The weight average molecular weight (Mw) of the hydroxystyrene resin is preferably 1,000 or more, more preferably 2,000 or more, particularly preferably 2,500 or more, preferably 10,000 or less, more preferably 8,000 or less, and particularly preferably 7,000 or less. By setting it as the said range, it is excellent in the coexistence of the high-sensitivity and the normal-temperature storage property of a varnish. The content of the hydroxystyrene resin is preferably 1 part by mass or more and 70 parts by mass or less, more preferably 10 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the polymer precursor containing a hetero ring. If it is this range, the pattern which does not flow after the heat processing after high temperature can be acquired with high sensitivity. The hydroxystyrene resin may be used singly or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Photoradical polymerization initiator> The composition of the present invention may further contain a photoradical polymerization initiator. When the composition contains a photo-radical polymerization initiator, the composition is applied to a semiconductor wafer or the like to form a composition layer, and then light is irradiated, thereby causing hardening by radicals, and the light irradiation portion can be formed. The solubility is lowered. Therefore, for example, the composition layer is exposed through a photomask having a pattern covering only the electrode portions, whereby it is possible to easily produce regions having different solubility depending on the pattern of the electrodes.

The photo-radical polymerization initiator is not particularly limited as long as it has a function of starting a polymerization reaction (cross-linking reaction) of the polymerizable compound, and can be appropriately selected from known photo-radical polymerization initiators. For example, it is preferred that the light from the ultraviolet region to the visible region is photosensitive. Alternatively, it may be an active agent that produces a reactive radical with a certain effect on the photoexcited sensitizer. As the photoradical polymerization initiator, it is preferred to contain at least one compound having a Mohr absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (preferably 330 nm to 500 nm). . The molar absorption coefficient of the compound can be determined by a known method. For example, it is preferably measured by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As a photoradical polymerization initiator, a known compound can be used without limitation, and examples thereof include a halogenated hydrocarbon derivative (for example, a triazine skeleton, a oxadiazole skeleton, a trihalomethyl group, etc.), a mercaptophosphine compound such as a mercaptophosphine oxide, an antimony compound such as a hexaarylbiimidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, an aminoacetophenone compound, Hydroxyacetophenone, azo compound, azide compound, metallocene compound, organoboron compound, iron aromatic hydrocarbon complex, and the like.

Examples of the halogenated hydrocarbon derivative having a triazine skeleton include a compound described in Japanese Society of Chemical Engineering (Bull. Chem. Soc. Japan), 42, 2924 (1969), and British Patent No. 1,888,492. A compound described in the specification, a compound described in JP-A-53-133428, a compound described in the specification of German Patent No. 3337024, and an organic chemical journal (J. Org. Chem, FC Schaefer, etc.) The compound described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound described in the publication No. 34920, and the compound described in the specification of U.S. Patent No. 4,212,976.

Examples of the compound described in the specification of U.S. Patent No. 4,212,976 include compounds having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorophenyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(1-naphthyl)-1,3,4-oxadiazole , 2-trichloromethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2 -Tribromomethyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2- Trichloromethyl-5-(4-chlorostyryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-methoxystyryl)-1,3, 4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyryl)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl- 1,3,4-oxadiazole, etc.).

In addition, as a photo-radical polymerization initiator other than the above, a compound described in Paragraph No. 0086 of JP-A-2015-087611, Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent No. The compounds described in the specification of Japanese Patent Publication No. Sho 57-6096, and the specification of U.S. Patent No. 3,615,455 are incorporated herein by reference.

The ketone compound may, for example, be a compound described in Paragraph No. 0087 of JP-A-2015-087611, which is incorporated herein by reference. Among the commercially available products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be suitably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an amino acetophenone-based initiator as described in JP-A-10-291969, and a sulfhydryl phosphine oxide-based initiator described in Japanese Patent No. 4,258,899 can be used. As the hydroxyacetophenone-based initiator, IRGACURE-184 (IRGACURE is a registered trademark), DAROCUR-1173, and IRGACURE-500 can be used. IRGACURE-2959, IRGACURE-127 (trade name: all manufactured by BASF). As the aminoacetophenone-based initiator, IRGACURE-907, IRGACURE-369, and IRGACURE-379 can be used as commercially available products (trade name: Made for BASF). As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which has a maximum absorption wavelength and a light source of 365 nm or 405 nm, can also be used. As the mercaptophosphine-based initiator, IRGACURE-819 or DAROCUR-TPO (trade name: all manufactured by BASF Corporation), which is a commercially available product, can be used. As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) and the like can be exemplified.

As the photoradical polymerization initiator, a ruthenium compound is more preferable. As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used. . Preferred examples of the hydrazine compound include 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3-propoxycarbonyl group. Iminobutan-2-one, 2-ethyloxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one, 2-phenyl Nonyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimido -1-Phenylpropan-1-one and the like. [化63]

As the ruthenium compound, "JCS Perkin II" (JCS Perkin II) (1979) pp. 1653-1660, "British Chemical Society, Berkin Journal II" (1979) Pp. 156-162, "Journal of Photopolymer Science and Technology" (1995, pp. 202-232), Japanese Patent Laid-Open No. 2000-66385, Japanese Patent Special Open 2000 The compound described in each of the publications of Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. Among the commercially available products, IRGACURE-OXE01 (manufactured by BASF Corporation), IRGACURE-OXE02 (manufactured by BASF Corporation), and N-1919 (manufactured by Adeco Co., Ltd.) can be suitably used. In addition, TR-PBG-304 (made by Changzhou Power Electronic New Materials Co., Ltd.), ADEKA ARCLUZ NCI-831, and ADEKA ARCLUZ NCI-930 (Adico) can also be used. Made by the company).

In addition, the compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is linked to the N-position of the carbazole ring, and the U.S. Patent No. 7,626,957, the disclosure of which is incorporated herein by reference. The ketone oxime compound described in Japanese Patent Laid-Open Publication No. 2010-15025, and the ketone oxime compound described in International Publication WO2009/131189, in the same molecule A compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. . In addition, the cyclic anthraquinone compound described in JP-A-2007-2320, and JP-A-2007-322744 can also be suitably used. Among the cyclic ruthenium compounds, the cyclic ruthenium compound condensed in the carbazole dye described in Japanese Patent Laid-Open Publication No. 2010-185072, and the Japanese Patent Publication No. 2010-185072 has high light absorption properties. It is preferable from the viewpoint of high sensitivity. In addition, a compound described in JP-A-2009-242469, which is a compound having an unsaturated bond at a specific site of a ruthenium compound, can be suitably used. Further, an anthracene compound having a fluorine atom can also be used. Specific examples of such a ruthenium compound include the compound described in JP-A-2010-262028, and the compound 24 and the compound 36 as described in paragraph 0345 of JP-A-2014-500852. The compound (C-3) and the like described in Paragraph No. 0101 of JP-A-2013-164471. Specific examples thereof include the following compounds. [化64] The ruthenium compound having a specific substituent as shown in Japanese Laid-Open Patent Publication No. 2007-269779, or the thioaryl group shown in Japanese Patent Laid-Open Publication No. 2009-191061肟 compounds, etc.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, Mercaptophosphine compound, phosphine oxide compound, metallocene compound, hydrazine compound, triaryl imidazole dimer, hydrazine compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene a compound of the group consisting of a benzene-iron complex and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound. More preferably, it is a trihalomethyltriazine compound, an α-amino ketone compound, a mercaptophosphine compound, a phosphine oxide compound, an anthraquinone compound, a triaryl imidazole dimer, an anthraquinone compound, a benzophenone compound, an acetophenone compound. Further, a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triaryl imidazole dimer, and a benzophenone compound are more preferable, and a ruthenium compound is preferably used.

When the composition contains a photoradical polymerization initiator, the content of the photoradical polymerization initiator is preferably from 0.1% by mass to 30% by mass, more preferably from 0.1% by mass to 20%, based on the total solid content of the composition. The mass%, more preferably 0.1% by mass to 10% by mass. The photoradical polymerization initiator may be used alone or in combination of two or more. When the photoradical polymerization initiator is two or more kinds, it is preferred that the total is in the above range.

<Photoacid generator> The composition in the present invention may further contain a photoacid generator. By containing a photoacid generator, an acid is generated in the exposed portion, and the solubility of the exposed portion in the alkaline aqueous solution is increased, so that it can be used as a positive type composition.

Examples of the photoacid generator include a quinonediazide compound, a phosphonium salt, a phosphonium salt, a diazonium salt, and a phosphonium salt. Among them, in view of exhibiting an excellent dissolution inhibiting effect and obtaining a composition having high sensitivity and a small film thickness, a quinonediazide compound is preferably used. Further, two or more photoacid generators may be contained. Thereby, the ratio of the dissolution rate of the exposed portion and the unexposed portion can be further increased, and a high-sensitivity positive composition can be obtained.

The quinonediazide compound may be one in which a sulfonic acid of quinonediazide is ester-bonded to a polyhydroxy compound, and a sulfonic acid of quinonediazide in a polyamine compound is sulfonamide bonded. The sulfonic acid of the quinonediazide in the polyhydroxypolyamine compound is ester-bonded and/or sulfonamide-bonded. By using such a quinonediazide compound, a positive composition which is sensitive to i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) which are ordinary ultraviolet light mercury lamps can be obtained. . In addition, all of the functional groups of the polyhydroxy compound, the polyamine compound, and the polyhydroxy polyamine compound may be substituted without quinonediazide, but it is preferred that two or more functional groups per molecule pass through Azide substitution. As an example, the following compounds are exemplified. [化65] In the compound, 1% to 10% of the total amount of Q may be a hydrogen atom, or 4% to 6% may be a hydrogen atom.

As the polyhydroxy compound, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP- may be mentioned. IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tri-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP , DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (above trade name, manufactured by Honshu Chemical Industry), BIR-OC, BIP-PC, BIR -PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (above, trade name, Asahi Organic Industry Manufactured), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diethyloxymethyl-pair Cresol, naphthol, tetrahydroxybenzophenone, methyl gallate, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry), novolac Resin or the like, but is not limited to these compounds.

Examples of the polyamine-based compound include 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4'-diaminodiphenyl ether, and 4,4'-diamino group. Diphenylmethane, 4,4'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide, etc., but are not limited to these compounds.

Further, examples of the polyhydroxy polyamine-based compound include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto. These compounds.

As the quinonediazide compound, any of a compound having a 5-naphthoquinonediazidesulfonyl group and a compound having a 4-naphthoquinonediazidesulfonyl group can be preferably used. A compound having both of these groups in the same molecule may also be used, and a compound having a different group may also be used in combination.

As a method of producing the quinonediazide compound, for example, a method of reacting 5-naphthoquinonediazidesulfonium chloride with a phenol compound in the presence of triethylamine can be mentioned. The method for synthesizing the phenol compound includes a method of reacting an α-(hydroxyphenyl)styrene derivative with a polyhydric phenol compound under an acidic catalyst.

The content of the photoacid generator is preferably from 3 parts by mass to 40 parts by mass based on 100 parts by mass of the polymer precursor containing a hetero ring. By setting the content of the photoacid generator to this range, higher sensitivity can be achieved. Further, a sensitizer or the like may be contained as needed. The photoacid generator may be used singly or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Thermal acid generator> The composition in the present invention may also contain a thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of the heterocyclic-containing polymer precursor and further enhances the mechanical properties of the cured film, and has an effect of promoting a crosslinking reaction of the following compound. It is at least one selected from the group consisting of a compound having a hydroxymethyl group, an alkoxymethyl group or a decyloxymethyl group, an epoxy compound, an oxetane compound, and a benzoxazine compound.

The thermal decomposition initiation temperature of the thermal acid generator is preferably from 50 ° C to 270 ° C, more preferably not more than 250 ° C. In addition, when drying (prebaking: about 70 ° C to 140 ° C) after the composition is applied to the substrate, the final heating after patterning by exposure and development (after no acid is generated) is selected ( When the acid is generated at a temperature of from about 100 ° C to about 400 ° C, the sensitivity at the time of development can be suppressed, which is preferable.

The acid produced by the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid or benzenesulfonic acid; an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid; and A halogenated alkyl sulfonic acid such as fluoromethanesulfonic acid or the like. An example of such a thermal acid generator is described in paragraph 0055 of JP-A-2013-072935.

In the case where the residual amount in the cured film is small and the physical properties of the cured film are not lowered, it is more preferable to produce an alkylsulfonic acid having 1 to 4 carbon atoms and a halogenated alkylsulfonic acid having 1 to 4 carbon atoms. Preferred is (4-hydroxyphenyl)dimethylhydrazine methanesulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylhydrazine methanesulfonate, benzyl methanesulfonate (4- Hydroxyphenyl)methylhydrazine, benzyl methanesulfonate (4-((methoxycarbonyl)oxy)phenyl)methylhydrazine, methanesulfonic acid (4-hydroxyphenyl)methyl ((2-A) Phenyl)methyl)anthracene, (4-hydroxyphenyl) dimethyl sulfonium trifluoromethanesulfonate, (4-((methoxycarbonyl)oxy)phenyl) dimethyl trifluoromethanesulfonate鋶, benzyl (4-hydroxyphenyl)methyl fluorene trifluoromethanesulfonate, benzyl (4-((methoxycarbonyl)oxy)phenyl)methyl fluorene trifluoromethanesulfonate, trifluoromethyl Sulfonic acid (4-hydroxyphenyl)methyl ((2-methylphenyl)methyl) fluorene, 3-(5-((propylsulfonyl)oxy)imino)thiophene-2 ( 5H)-Subunit)-2-(o-tolyl)propanenitrile, 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

Further, the compound described in Paragraph No. 0059 of JP-A-2013-167742 is also preferable as a thermal acid generator.

When the thermal acid generator is used, the content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, based on 100 parts by mass of the polymer precursor containing a hetero ring. By containing 0.01 part by mass or more, the crosslinking reaction and the cyclization of the polymer precursor containing a hetero ring are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. In addition, from the viewpoint of electrical insulation of the cured film, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less. The thermal acid generator may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Thermal Radical Polymerization Starter> The composition in the present invention may also contain a thermal radical polymerization initiator. As the thermal radical polymerization initiator, a known thermal radical polymerization initiator can be used. The thermal radical polymerization initiator is a compound which generates radicals by thermal energy and starts or promotes polymerization of a polymerizable compound. When the cyclization reaction of the heterocyclic-containing polymer precursor is carried out by adding a thermal radical polymerization initiator, the polymerization reaction of the polymerizable compound can be carried out. Further, when the polymer precursor containing a hetero ring contains an ethylenically unsaturated bond, the cyclization of the heterocyclic-containing polymer precursor can also be carried out together with the polymerization reaction of the heterocyclic-containing polymer precursor. Achieve higher heat resistance. Examples of the thermal radical polymerization initiator include aromatic ketones, phosphonium salt compounds, peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, oxazine compounds, and porphyrin. a metal compound, an active ester compound, a compound having a carbon halogen bond, an azo compound, or the like. Among them, a peroxide or an azo compound is more preferred, and a peroxide is particularly preferred. The 10-hour half-life temperature of the thermal radical polymerization initiator used in the present invention is preferably from 90 ° C to 130 ° C, more preferably from 100 ° C to 120 ° C. Specifically, the compound described in Paragraph No. 0074 to Paragraph No. 0118 of JP-A-2008-63554 is mentioned. Among the commercially available products, Perbutyl Z and Percumyl D (manufactured by Nippon Oil Co., Ltd.) can be suitably used.

When the composition contains a thermal radical polymerization initiator, the content of the thermal radical polymerization initiator is preferably from 0.1% by mass to 50% by mass, more preferably from 0.1% by mass to 30%, based on the total solid content of the composition. The mass% is particularly preferably from 0.1% by mass to 20% by mass. In addition, it is preferably contained in an amount of from 0.1 part by mass to 50 parts by mass, more preferably from 0.5 part by mass to 30 parts by mass, based on 100 parts by mass of the polymerizable compound. According to this aspect, it is easy to form a cured film which is more excellent in heat resistance. The thermal radical polymerization initiator may be used alone or in combination of two or more. When the number of the thermal radical polymerization initiators is two or more, it is preferred that the total is in the above range.

<Anticorrosive Agent> In the composition of the present invention, it is preferred to add an anticorrosive agent. The anticorrosive agent is added for the purpose of preventing the ions from flowing out of the metal wiring. For example, the rust preventive agent described in paragraph 0094 of JP-A-2013-15701, Japanese Patent Laid-Open No. 2009-283711 The compound described in Paragraph No. 0073 to Paragraph No. 0076 of the Japanese Patent Publication No. JP-A-2011-59656, Paragraph No. 0052, Paragraph No. 0114, Paragraph No. 0116 of JP-A-2012-194520 And the compound described in Paragraph No. 0118. Among them, a compound having a triazole ring or a compound having a tetrazole ring can be preferably used, more preferably 1,2,4-triazole, 1,2,3-benzotriazole, 5-methyl-1H. - benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, most preferably 1H-tetrazole. When the anticorrosive agent is used, the content of the anticorrosive agent is preferably in the range of 0.1 part by mass to 10 parts by mass, more preferably 0.2 part by mass to 5 parts by mass, based on 100 parts by mass of the polymer precursor containing the hetero ring. The anticorrosive agent may be used singly or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Metal adhesion improver> The composition in the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode or a wiring. Examples of the metal adhesion improver include those described in paragraphs 0046 to 0049 of JP-A-2014-186186, and paragraphs 0032 to 0043 of JP-A-2013-072935. a thioether compound. Further, as the metal adhesion improver, the following compounds can also be exemplified. [化66] When a metal adhesion improver is used, the content of the metal adhesion improver is preferably from 0.1 part by mass to 30 parts by mass, more preferably from 0.5 part by mass to 15 parts by mass, per 100 parts by mass of the polyimide intermediate precursor. The scope of the share. By setting it as 0.1 mass part or more, the adhesiveness of the film after thermosetting and metal is favorable, and it is set as 30 mass parts or less, and the heat resistance and mechanical characteristics of the film after hardening are favorable. The metal adhesion improver may be used alone or in combination of two or more. When two or more types are used, it is preferable to add up to the above range.

<Centane Coupling Agent> The composition in the present invention preferably contains a decane coupling agent in terms of improving the adhesion to the substrate. Examples of the decane coupling agent include those described in paragraphs 0062 to 0063 of JP-A-2014-191002, and paragraphs 0063 to 0071 of WO2011/080992A1. The compound described in Paragraph No. 0060 to Paragraph 0061 of JP-A-2014-191252, and the compound described in paragraph No. 0045 to paragraph 0052 of JP-A-2014-41264, International Publication WO2014/ The compound described in Paragraph No. 0055 of 097594. Further, it is also preferred to use two or more different decane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. When a decane coupling agent is used, the content of the decane coupling agent is preferably in the range of 0.1 part by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, per 100 parts by mass of the polymer precursor containing the hetero ring. range. When it is 0.1 part by mass or more, it is possible to provide more sufficient adhesion to the substrate, and if it is 20 parts by mass or less, it is possible to further suppress problems such as an increase in viscosity at the time of storage at room temperature. The decane coupling agent may be used singly or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Solution accelerator> When the composition in the present invention is a positive type using an alkaline developer, it is preferred to add a dissolution promoter (a compound which promotes solubility) from the viewpoint of improving the sensitivity. Examples of the dissolution promoter include low molecular weight phenols (for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, and BisRS-3P (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR - PC, BIR-PTBP, BIR-BIPC-F (the above is a trade name, manufactured by Asahi Organic Materials Co., Ltd.), and the phenols described in paragraphs 0056 to 0062 of JP-A-2013-152381 A sulfoximine derivative (for example, a compound described in Paragraph No. 0059 of JP-A-2011-164454). When a dissolution promoter is used, the content of the dissolution promoter is preferably in the range of 0.1 part by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, per 100 parts by mass of the polymer precursor containing a hetero ring. range. The dissolution promoter may be used singly or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Dissolution inhibitor> When the composition in the present invention is a positive type using an alkaline developer, a dissolution inhibitor (a compound which inhibits solubility) may be contained in order to adjust the solubility to the alkaline developer. As such a compound, a phosphonium salt, a diaryl compound, and a tetraalkylammonium salt are preferable. Examples of the onium salt include a phosphonium salt such as a sulfonium salt such as a diarylsulfonium salt or a sulfonium salt such as a phosphonium salt such as a triarylsulfonium salt or a phosphonium salt or an aryldiazonium salt. As the diaryl compound, two aryl groups such as a diaryl urea, a diaryl hydrazine, a diaryl ketone, a diaryl ether, a diaryl propane, and a diaryl hexafluoropropane are bonded via a bonding group. As the aryl group, a phenyl group is preferred. The tetraalkylammonium salt may, for example, be a halogenated tetraalkylammonium group in which the alkyl group is a methyl group or an ethyl group.

Examples of the good dissolution inhibitory effect in the above include a diarylsulfonium salt, a diaryl urea, a diarylsulfonium, a tetramethylammonium halide, and the like. Examples of the diaryl urea include a diphenyl group. Examples of the halogenated tetramethylammonium such as urea or dimethyldiphenylurea include tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide.

Among them, a diarylsulfonium salt represented by the formula (Inh) is preferred. [67] (Inh) (wherein, X ^- represents a counter anion, and R ⁷ and R ⁸ each independently represent a monovalent organic group, and a and b are each independently an integer of 0 to 5)

Examples of the counter anion X ^- include a nitrate ion, a boron tetrafluoride ion, a perchlorate ion, a triflate ion, a p-toluenesulfonate ion, a thiocyanate ion, a chloride ion, a bromide ion, and an iodide ion. Wait.

As the diarylsulfonium salt, for example, diphenylphosphonium nitrate, bis(p-tert-butylphenyl)phosphonium nitrate, diphenylsulfonium trifluoromethanesulfonate, and bis(p-tert-butyl) can be used. Phenyl)indole trifluoromethanesulfonate, diphenylphosphonium bromide, diphenylphosphonium chlorate, diphenylphosphonium iodate, diphenylphosphonium-8-anilinonaphthalene-1-sulfonic acid Salt and so on. Among these, diphenylphosphonium nitrate, diphenylsulfonium trifluoromethanesulfonate, and diphenylphosphonium-8-anilinonaphthalene-1-sulfonate have high effects and can be preferably enumerated.

When the dissolution inhibitor is contained, the content of the dissolution inhibitor is preferably from 0.1 part by mass to 20 parts by mass per 100 parts by mass of the polymer precursor containing a hetero ring, from the viewpoint of the sensitivity and the allowable range of the development time. It is preferably from 0.1 part by mass to 15 parts by mass, more preferably from 0.5 part by mass to 10 parts by mass. The dissolution inhibitor may be used singly or in combination of two or more. When two or more types are used, it is preferable that the total amount is the above range.

<Sensitizing dye> The composition in the present invention may also contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye which is in an electronically excited state is brought into contact with an amine generator, a thermal radical polymerization initiator, a photoradical polymerization initiator, and the like, and causes an action of electron movement, energy movement, and heat generation. Thereby, the amine generator, the thermal radical polymerization initiator, and the photoradical polymerization initiator are chemically changed to be decomposed, and a radical, an acid or a base is generated.

Examples of preferred sensitizing dyes include those belonging to the following compounds and having a maximum absorption wavelength in a region of 300 nm to 450 nm. For example, polynuclear aromatics (for example, phenanthrene, anthracene, anthracene, anthracene, triphenylene, 9,10-dialkyloxyanthracene), xanthenes (for example, luciferin, eosin, erythromycin, and if Danming B, Bengal Rose Red), thioxanthone (such as 2,4-diethylthiazinone), cyanine (such as thiacarbocyanine, oxacarbocyanine), merocyanine Classes (eg, merocyanine, carbocyanine), thiazides (eg, thiazide, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavon, acridine flavin), 蒽Terpenoids (eg, hydrazine), squaric acid guanidine salts (eg, squaric acid ylide), coumarin (eg 7-diethylamino-4-methylcoumarin), benzene Vinyl benzenes, distyryl benzenes, oxazoles, and the like.

Among them, in the present invention, from the viewpoint of initial efficiency, it is preferred to use a polynuclear aromatic group (for example, phenanthrene, anthracene, anthracene, anthracene, triphenylene), thioxanthone or distyrylbenzene. The class, styrylbenzene, more preferably a compound having an anthracene skeleton. Specific examples of the specific compound include 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and the like.

When the composition contains a sensitizing dye, the content of the sensitizing dye is preferably from 0.01% by mass to 20% by mass, more preferably from 0.1% by mass to 15% by mass, even more preferably 0.5% based on the total solid content of the composition. Mass% to 10% by mass. The sensitizing dye may be used alone or in combination of two or more.

<Chain Transfer Agent> The composition in the present invention may also contain a chain transfer agent. The chain transfer agent is defined, for example, in the third edition of the Polymer Dictionary (edited by the Society of Polymers, 2005) on pages 683 to 684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, or GeH in the molecule can be used. The chain transfer agents provide hydrogen to the low-activity radical species to form free radicals, or are oxidized and then deprotonated, thereby generating free radicals. In particular, a thiol compound (for example, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 3-mercaptotriazole, 5-mercaptotetrazole, or 5-mercaptotetrazole may be preferably used. Wait).

When the composition contains a chain transfer agent, the content of the chain transfer agent is preferably from 0.01 part by mass to 20 parts by mass, more preferably from 1 part by mass to 10 parts by mass, based on 100 parts by mass of the total solid content of the composition. It is preferably 1 part by mass to 5 parts by mass. The chain transfer agent may be used alone or in combination of two or more. When the chain transfer agent is two or more kinds, it is preferred that the total amount is the above range.

<Polymerization inhibitor> In order to prevent unnecessary thermal polymerization of a heterocyclic-containing polymer precursor and a radical polymerizable compound during or during the production process, the composition of the present invention preferably contains a small amount of polymerization. Inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, p-tert-butylcatechol, benzoquinone, 4 can be suitably cited. 4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso -N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid , glycol ether diamine tetraacetic acid, 2,6-di-t-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2- Nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamino)phenol, N-nitroso-N-(1-naphthyl)hydroxyl ammonium Salt, bis(4-hydroxy-3,5-t-butyl)phenylmethane. When the composition contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably from 0.01% by mass to 5% by mass based on the total solid content of the composition. The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is two or more kinds, it is preferred that the total is in the above range.

<Interacting Agent> In the composition of the present invention, various surfactants may be added from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and an anthrone-based surfactant can be used. In particular, by including a fluorine-based surfactant, the liquid properties (especially fluidity) at the time of preparation as a coating liquid are further improved, so that the uniformity of the coating thickness or the liquid-saving property can be further improved. When a film is formed using a coating liquid containing a fluorine-based surfactant, the interfacial tension between the surface to be coated and the coating liquid is lowered, whereby the wettability to the surface to be coated is improved, and the coating is applied. The coating properties of the surface are improved. Therefore, even when a film having a thickness of about several μm is formed with a small amount of liquid, it is effective to form a film having a uniform thickness with a small thickness unevenness.

The fluorine content of the fluorine-based surfactant is suitably from 3% by mass to 40% by mass, more preferably from 5% by mass to 30% by mass, even more preferably from 7% by mass to 25% by mass. The fluorine-containing surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film or the liquid-saving property, and the solubility is also good. Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, and Megafac. F141, Megafac F142, Megafac F143, Megafac F144, Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781 (above, DiCai (DIC) (share) manufacturing), Fluorad FC430 , Fluorad FC431, Fluorad FC171 (above, Sumitomo 3M (share)), Surflon S-382, Surflon SC-101 , Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC1068, Surflon SC-381, sand Surflon SC-383, Sha Fulong (Su Rflon) S393, Surfon KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA). As the fluorine-based surfactant, a block polymer can also be used. Specific examples thereof include a compound described in JP-A-2011-89090. Further, the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention. [化68] The weight average molecular weight of the compound is, for example, 14,000.

Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, Glycerol ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethyl b Diol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10 manufactured by BASF, Pluronic L31, Pullul Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304, Tyrone Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solsperse 20000 (Lubrizol, Japan) ) (shares) Wait. In addition, Pionin D-6112-W manufactured by Takeshi Oil Co., Ltd., and NCW-101, NCW-1001, and NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. can also be used.

Specific examples of the cation-based surfactant include a phthalocyanine derivative (trade name: Efka (EFKA)-745, manufactured by Morishita Industry Co., Ltd.), and an organic siloxane polymer KP341 (Shin-Etsu Chemical Industry) (Made) manufacturing), (meth)acrylic (co)polymer Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 ( Gongrongshe Chemical (share) manufacturing), W001 (Yu Shang (share) manufacturing) and so on.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

Examples of the fluorenone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, and Toray ketone manufactured by Toray Dow Corning Co., Ltd. (Toray Silicone) DC11PA", "Toray Silicone SH21PA", "Toray Silicone SH28PA", "Toray Silicone SH29PA", "Toray Ketone (Toray) Silicone) SH30PA", "Toray Silicone SH8400", "TSF-4440", "TSF-4300", "TSF-4445", "TSF-" manufactured by Momentive Performance Materials 4460", "TSF-4452", "KP341", "KF6001", "KF6002" manufactured by Shintosu Silicon Co., Ltd., "BYK307" and "BYK323" manufactured by BYK Chemie , "BYK330" and so on.

When the composition contains a surfactant, the content of the surfactant is preferably 0.001% by mass to 2.0% by mass, and more preferably 0.005% by mass to 1.0% by mass based on the total solid content of the composition. The surfactant may be used alone or in combination of two or more. When the amount of the surfactant is two or more, it is preferable that the total amount is the above range.

<Higher Fatty Acid Derivatives and the like> In the composition of the present invention, in order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenylamine may be added and the like. It is biased toward the surface of the composition during the drying process after coating. When the composition contains a higher fatty acid derivative or the like, the content of the higher fatty acid derivative or the like is preferably 0.1% by mass to 10% by mass based on the total solid content of the composition. The higher fatty acid derivative or the like may be used alone or in combination of two or more. When two or more kinds of higher fatty acid derivatives and the like are used, it is preferred that the total is in the above range.

<Solvent> When the composition of the present invention is formed into a layer by coating, it is preferred to prepare a solvent. The solvent can be used without any limitation as long as the composition can be formed into a layer. The solvent to be used in the composition of the present invention may, for example, be ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate or butyl propionate. Isobutyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyl acetate (Example: methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, B) Methyl oxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkyloxypropionate (for example: methyl 3-alkyloxypropionate, 3-alkyloxypropionic acid) Ethyl ester or the like (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2- Alkyl alkyl propionate (for example: methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (for example 2- Methyl methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropane Propyl ester, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropanoate and 2-alkyloxy-2- Ethyl methacrylate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and, as the ether, for example, diethyl Diol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, and the like, and as ketones, for example Methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone are exemplified, and, as an aromatic hydrocarbon, for example, Suitably, toluene, xylene, anisole, limonene, etc. are listed. It is a sulfoxide-based, can suitably include dimethyl sulfoxide.

From the viewpoint of improvement in the state of the coated surface, etc., a form in which two or more kinds of solvents are mixed is also preferable. Among them, preferred is a mixed solution comprising methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethyl phthalate. Alcohol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl azine, ethyl carbitol Two or more of an acid ester, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate. It is particularly preferred to use dimethyl hydrazine and γ-butyrolactone in combination.

When the composition contains a solvent, the content of the solvent is preferably such that the total solid content of the composition is from 5% by mass to 80% by mass, and more preferably from 5% by mass to 70%. The mass%, and more preferably 10% by mass to 60% by mass. The solvent may be used alone or in combination of two or more. When the solvent is two or more, it is preferred that the total is in the above range. Further, in terms of film strength, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, relative to the total mass of the composition The content of N,N-dimethylformamide is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.5% by mass, and particularly preferably less than 0.1% by mass.

<Other Additives> The composition of the present invention may be formulated with various additives such as inorganic particles, hardeners, hardening catalysts, fillers, antioxidants, ultraviolet absorbers, and anti-drugs as needed within the scope of the effects of the present invention. Coagulant, etc. When these additives are blended, the total amount of the additives is preferably 3% by mass or less of the solid content of the composition.

The moisture content of the composition in the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, still more preferably less than 0.6% by mass, from the viewpoint of coating the surface state.

From the viewpoint of the insulating property, the metal content of the composition in the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, still more preferably less than 0.5 ppm by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are contained, it is preferred that the total of the metals is in the range. In addition, as a method of reducing the metal impurities which are unintentionally contained in the composition, a method of selecting a raw material having a small metal content as a raw material constituting the composition, and filtering the raw material constituting the composition in a device may be mentioned. The lining is carried out by using polytetrafluoroethylene or the like to carry out distillation under conditions which suppress contamination as much as possible.

The content of the halogen atom of the composition in the present invention is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. Among them, the halogen ion is preferably present in an amount of less than 5 ppm by mass, more preferably less than 1 ppm by mass, still more preferably less than 0.5 ppm by mass. Examples of the halogen atom include a chlorine atom and a bromine atom. Preferably, the total of the chlorine atom and the bromine atom, or the chloride ion and the bromide ion are each in the above range.

<Preparation of Composition> The composition in the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by a conventionally known method. Further, it is preferred to perform filtration using a filter for the purpose of removing foreign matter such as dust or fine particles in the composition. The pore diameter of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.1 μm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene or nylon. The filter can also be washed using a solvent previously prepared with an organic solvent. In the filter filtration step, a plurality of filters can be used in series or in parallel. When using a variety of filters, it is also possible to combine filters with different apertures and/or materials. In addition, various materials can be filtered multiple times, and the step of multiple filtration can also be a cyclic filtration step. Further, the filtration may be carried out under pressure, and the pressure of the pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to filtration using a filter, an adsorbent material may also be used for impurity removal. Alternatively, the filtration using the filter may be combined with the removal of impurities using the adsorbent material. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as cerium oxide gel or zeolite or an organic adsorbent such as activated carbon can be used.

<Application> The method for producing a cured film of the present invention can be preferably used in the field of an insulating film for a semiconductor element, an interlayer insulating film for a rewiring layer, and the like. That is, the present invention also discloses a method of producing a semiconductor element including the method for producing a cured film of the present invention. In particular, since it has good resolution, it can be preferably used in the production of an interlayer insulating film for a rewiring layer in a three-dimensional mounting element. That is, the present invention also discloses a method for producing an interlayer insulating film for a rewiring layer including the method for producing a cured film of the present invention. Further, a cured film obtained by the method for producing a cured film of the present invention and a semiconductor element obtained by the method for producing a cured film of the present invention are disclosed. Further, the cured film produced by the present invention can also be used for a photoresist for electronics (galvanic resist, etch resist, solder top resist) Wait. In addition, the cured film produced by the present invention can also be used for the manufacture of layouts such as lithographic or screen layouts, for the use of etching of formed parts, and for the protection of paints and dielectric layers in electronics, especially in microelectronics. Manufacturing, etc.

Next, an embodiment in which the composition is used for a semiconductor element of an interlayer insulating film for a wiring layer will be described. The semiconductor element 100 shown in FIG. 1 is a so-called three-dimensional mounting element, and a laminated body 101 in which a plurality of semiconductor devices (semiconductor wafer) 101a to semiconductor device (semiconductor wafer) 101d are laminated is disposed on the wiring substrate 120. In this embodiment, the number of layers of the semiconductor device (semiconductor wafer) is four, and the number of layers of the semiconductor device (semiconductor wafer) is not particularly limited. For example, it may be two layers. 8 layers, 16 layers, 32 layers, and the like. In addition, it can also be 1 layer.

Each of the plurality of semiconductor devices 101a to 101d includes a semiconductor wafer such as a germanium substrate. The uppermost semiconductor device 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor device 101b to the semiconductor device 101d have a through electrode 102b to a through electrode 102d, and connection pads (not shown) integrally provided on the through electrodes are provided on both surfaces of each semiconductor device.

The laminated body 101 has a structure in which a semiconductor device 101a having no through electrodes and a semiconductor device 101b to a semiconductor device 101d having a through electrode 102b to a through electrode 102d are flip-chip bonded. That is, the electrode pads of the semiconductor device 101a having no through electrodes and the connection pads on the side of the semiconductor device 101a of the semiconductor device 101b having the through electrodes 102b adjacent thereto are connected by metal bumps 103a such as solder bumps, and have a through-hole The connection pad on the other side of the semiconductor device 101b of the electrode 102b and the connection pad on the side of the semiconductor device 101b of the semiconductor device 101c having the through electrode 102c adjacent thereto are connected by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor device 101c having the through electrode 102c and the connection pad on the side of the semiconductor device 101c having the semiconductor device 101d having the through electrode 102d adjacent thereto are made of a metal bump 103c such as a solder bump. Come connect.

The underfill layer 110 is formed in a gap between each of the semiconductor devices 101a to 101d, and each of the semiconductor devices 101a to 101d is laminated via the underfill layer 110.

The laminated body 101 is laminated on the wiring substrate 120. As the wiring substrate 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a substrate is used. As the wiring substrate 120 to which the resin substrate is applied, a multilayer copper clad laminate (multilayer printed wiring board) or the like can be given.

A surface electrode 120a is provided on one surface of the wiring substrate 120. An insulating layer 115 on which the rewiring layer 105 is formed is disposed between the wiring substrate 120 and the laminated body 101, and the wiring substrate 120 and the laminated body 101 are electrically connected via the rewiring layer 105. The insulating layer 115 is formed by using the photosensitive resin composition of the present invention. In other words, one end of the rewiring layer 105 is connected to the electrode pad formed on the surface on the side of the rewiring layer 105 of the semiconductor device 101d via the metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump. Further, an underfill layer 110a is formed between the insulating layer 115 and the laminated body 101. Further, an underfill layer 110b is formed between the insulating layer 115 and the wiring substrate 120.

In addition to the above, the cured film produced by the present invention can be widely used in various applications using polyimine or polybenzoxazole. In addition, since the polyimide film or the polybenzoxazole is heat-resistant, the cured film produced by the present invention can be suitably used as a transparent plastic substrate for a display device such as a liquid crystal display or an electronic paper, an automobile part, or a heat-resistant paint. , coating agent, film use. [Examples]

Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts, the ratios, the treatment contents, the treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Measurement Method of Weight Average Molecular Weight (Mw) × Number Average Molecular Weight (Mn)> Mw and Mn are polystyrene-converted values measured by Gel Permeation Chromatography (GPC), and the following methods are used. And measured. HLC-8220 (manufactured by Tosoh Co., Ltd.) was used as a measuring device, and Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 ( Tosoh (manufactured by Tosoh) as a pipe string. Further, the eluate was measured using tetrahydrofuran (THF) at a flow rate of 0.35 mL/min at 40 °C. The detection was performed using an ultraviolet (UV) 254 nm detector. Further, as a measurement sample, a sample in which a heterocyclic-containing polymer precursor was diluted with THF to 0.1% by mass was used.

(Synthesis Example 1 Synthesis of PIp-A) 21.2 g of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 18.1 g of 2-hydroxyethyl methacrylate Mixing 0.05 g of hydroquinone, 23.9 g of pyridine, and 150 mL of diethylene glycol diglyme, and stirring at 60 ° C for 2 hours to produce 4,4'-oxydi-o-benzene Diester of dicarboxylic acid and 2-hydroxyethyl methacrylate. Then, the reaction mixture was cooled to -10 ° C while maintaining the temperature at -10 ° C ± 4 ° C, and 17.1 g of SOCl _{2 was} added over 60 minutes. After dilution with 50 mL of N-methylpyrrolidone, 11.7 g of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N at -10 °C ± 4 °C for 60 minutes. A solution of -methylpyrrolidone was added dropwise to the reaction mixture, and the mixture was stirred for 2 hours. Then, the polyethyleneimine precursor was precipitated by putting into 6 liters of water, and the water-polyimine precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimine precursor was filtered, and again poured into 4 liters of water, stirred for 30 minutes, and filtered again. Then, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure. The polyimine precursor had a weight average molecular weight of 16,000, a number average molecular weight of 7,620, and a degree of dispersion of 2.1.

<Synthesis Example 2 Synthesis of PIp-B> 10.5 g of pyromellitic dianhydride, 10.0 g of 4,4'-diaminodiphenyl ether, 4.0 g of pyridine, and 150 mL of N-methyl group were used. The 2-pyrrolidone was mixed and stirred at a temperature of 60 ° C for 3 hours. Then, the polyethyleneimine precursor was precipitated by putting into 6 liters of water, and the water-polyimine precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimine precursor was filtered, re-introduced into 6 liters of water, stirred for 30 minutes, and filtered again. Then, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure. The polyimine precursor had a weight average molecular weight of 20,000, a number average molecular weight of 8,000, and a degree of dispersion of 2.5.

<Synthesis Example 3 Synthesis of PBp-D> 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 100 mL of N-methyl-2-pyrrolidone. Stir and dissolve. Then, while maintaining the temperature at 0 ° C to 5 ° C, 8.00 g of octane ruthenium chloride was added dropwise over 10 minutes, and stirring was continued for 60 minutes. Then, the polybenzoxazole precursor was precipitated by putting into 6 liters of water, and the water-polybenzoxazole precursor mixture was stirred at 5,000 rpm for 15 minutes. The polybenzoxazole precursor was filtered, re-introduced into 6 liters of water and stirred for 30 minutes and filtered again. Then, the obtained polybenzoxazole precursor was dried at 45 ° C for 3 days under reduced pressure. The polybenzoxazole precursor had a weight average molecular weight of 11,500, a number average molecular weight of 6,800, and a degree of dispersion of 1.7.

<Synthesis Example 4 Synthesis of PBp-E> In Synthesis Example 3, polybenzoxazole was obtained in the same manner except that 4,4'-oxybenzophenone chloride was changed to 11.21 g of octane dichloride. Precursor. The polybenzoxazole precursor had a weight average molecular weight of 15,000, a number average molecular weight of 7,100, and a degree of dispersion of 2.1.

<Synthesis Example 5 Synthesis of PB-F> In Synthesis Example 3, a polybenzoxazole precursor was obtained in the same manner except that octane ruthenium chloride was changed to 8.55 g of ruthenium dichloride. The obtained precursor was dissolved in 100 mL of N-methyl-2-pyrrolidone, and 100 mg of p-toluenesulfonic acid was added thereto, and the mixture was stirred at 200 ° C for 48 hours to complete the oxazole. Then, the polybenzoxazole was precipitated by putting into 6 liters of water, and the water-polybenzoxazole mixture was stirred at 5,000 rpm for 15 minutes. The polybenzoxazole was filtered off, poured again into 6 liters of water, stirred for 30 minutes, and filtered again. Then, the obtained polybenzoxazole was dried at 45 ° C for 3 days under reduced pressure. The polybenzoxazole had a weight average molecular weight of 17,500, a number average molecular weight of 10,000, and a degree of dispersion of 1.8.

<Synthesis Example 6 PIp-C> In Synthesis Example 1, except that 21.2 g of 4,4'-oxydiphthalic dianhydride was changed to 20.1 g of diphenyl-3,3',4,4 In addition to the tetracarboxylic dianhydride, a polyimine precursor was obtained in the same manner. 20.1 g of diphenyl-3,3',4,4'-tetracarboxylic dianhydride (dried at 140 ° C for 12 hours), 18.1 g of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone 23.9 g of pyridine and 150 mL of N-methylpyrrolidone were mixed and stirred at 60 ° C for 2 hours to produce 4,4'-oxydiphthalic acid and methacrylic acid-2- a diester of hydroxyethyl ester. Then, the reaction mixture was cooled to -10 ° C while maintaining the temperature at -10 ° C ± 4 ° C, and 17.1 g of SOCl _{2 was} added over 60 minutes. After dilution with 50 mL of N-methylpyrrolidone, 11.7 g of 4,4'-diaminodiphenyl ether was dissolved in 100 mL of N at -10 °C ± 4 °C for 60 minutes. A solution of -methylpyrrolidone was added dropwise to the reaction mixture, and the mixture was stirred for 2 hours. Then, 6 liters of water was charged to precipitate the polyimine precursor, and the water-polyimine precursor mixture was stirred at 5,000 rpm for 15 minutes. The polyimine precursor was filtered, and again poured into 4 liters of water, stirred for 30 minutes, and filtered again. Then, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure. The polyimine precursor had a weight average molecular weight of 15,000, a number average molecular weight of 6,820, and a degree of dispersion of 2.2.

[化69]

<Examples and Comparative Examples> The components described below were mixed to prepare a uniform solution to prepare a composition (coating liquid). <<Composition of Composition>> Polymer precursor containing a hetero ring: mass % shown in Table 6 or Table 7 Amine generator: mass % shown in Table 6 or Table 7 Polymerization initiator: Table 6 or Table 7 % by mass: Crosslinking agent: mass % shown in Table 6 or Table 7 Solvent: mass % shown in Table 6 or Table 7 Further, in Example 1, "PIp-A" of a polymer precursor containing a hetero ring The type of the precursor is indicated, and the value of "33" indicates the amount of the composition (unit: mass%). The same applies to other ingredients. The same applies to the other examples and comparative examples.

[Table 6]

[Table 7]

[化70] The amine production temperature of TBG1 was 150 ° C and pKa1 = 1.9. The amine production temperature of TBG2 was 150 ° C and pKa1 = 1.9. The amine production temperature of TBG3 was 150 ° C and pKa1 = 1.9. The amine production temperature of TBG4 was 145 °C. The amine production temperature of TBG5 was 150 °C. The amine production temperature of TBG6 was 180 °C.

[71] Ini1 is IRGACURE-OXE01 manufactured by BASF. Ini2 is IRGACURE-OXE02 manufactured by BASF. Ini3 was synthesized by the method described in Synthesis Example 4 of International Publication WO05/069075. Ini4 is an IRGACURE 784 made by BASF.

Slv1: γ-butyrolactone slv2: dimethyl azine slv3: N-methyl-2-pyrrolidone

[化72] Link5 Link1 has a molecular weight of 330 and is 4G manufactured by Shin-Nakamura Chemical Industry. Link2 has a molecular weight of 536 and is 9G manufactured by Shin-Nakamura Chemical Industry. Link3 has a molecular weight of 1136 and is 23G manufactured by Shin-Nakamura Chemical Industry. The molecular weight of link 4 is 318 and it is T2058 manufactured by Tokyo Chemical Industry Co., Ltd. The molecular weight of link 5 is 168, and it is B1525 manufactured by Tokyo Chemical Industry Co., Ltd. The molecular weight of link6 is 951.

<Amount of Amine> The amount of the amine in the cured film was quantified using a gas chromatograph (manufactured by Agilent) connected to a headspace sampler under the following conditions. The composition described in Table 6 or Table 7 was spin-coated at 4 rpm on a 4 吋矽 wafer (2.5 cm in a crucible), and heated on a hot plate at 100 ° C for 2 minutes to form a film. The obtained wafer was heat-hardened under the conditions described in Table 6 or Table 7 on a hot plate under a nitrogen stream. Here, the heating temperature in Table 6 or Table 7 means the highest heating temperature at the time of heat curing, and the heating time means the heating time after reaching the maximum heating temperature. Further, the temperature at the start of temperature rise was 25 °C. The resulting wafer was divided, placed in a 20 mL vial, and the components in the cured film were volatilized at 230 ° C for 7 minutes in a headspace sampler. The volatilized component was introduced into a gas chromatograph (manufactured by Agilent, Inc.), and heated at 150 ° C for 5 minutes using a capillary column HP-1MS (manufactured by Agilent Technologies), and then heated at a temperature elevation rate of 5 ° C / min. The separation was carried out while heating at 230 ° C for 5 minutes, and was detected by a detector (Flame Ionization Detector (FID)) (manufactured by Agilent Technologies). The amine content in the cured film was calculated from the peak area of the obtained amine and the standard curve of the separately prepared amine. Further, various amounts of the corresponding amines were weighed into a vial and measured by the same conditions as the sample, and a standard curve was prepared based on the obtained peak area and the weighing value.

<Corrosion Resistance> The composition described in Table 6 or Table 7 was spin-coated at 1,000 rpm on a 4-inch wafer on which copper was deposited, and heated on a hot plate at 100 ° C for 2 minutes to form a film. The obtained wafer was heat-hardened under the conditions described in Table 6 or Table 7 on a hot plate under a nitrogen stream. After hardening, the obtained wafer was placed under the conditions of a temperature of 85 ° C and a relative humidity of 85%, and the time until the surface of the copper was colored was measured. Coloring was confirmed by visual inspection. The corrosion resistance was evaluated as follows. A: No coloring was observed even after more than 3 hours. B: Coloring was observed within 1 hour and 3 hours. C: Coloring was observed within 1 hour.

<Chemical Resistance> The composition described in Table 6 or Table 7 was spin-coated on a 4-inch wafer at 1,000 rpm, and heated on a hot plate at 100 ° C for 2 minutes to form a film. The obtained wafer was heat-hardened under the conditions described in Table 6 or Table 7 on a hot plate under a nitrogen stream. After hardening, the obtained wafer was immersed in N-methyl-2-pyrrolidone for 3 hours, washed with isopropyl alcohol, and air-dried. The presence or absence of cracks in the cured film of the obtained wafer was visually observed. The chemical resistance was evaluated as follows. A: No crack was observed in the entire surface of the wafer. B: Crack was observed in the part of the wafer. C: Crack was observed in the entire surface of the wafer.

<Outgassing property> The composition described in Table 6 or Table 7 was spin-coated on a 4-inch wafer at 1,000 rpm, and heated on a hot plate at 100 ° C for 2 minutes to form a film. The obtained wafer was heat-hardened under the conditions described in Table 6 or Table 7 on a hot plate under a nitrogen stream. After the curing, the obtained wafer was heated to a temperature of 350 ° C at 10 ° C / min under a nitrogen stream by a thermogravimetric analyzer (Q-500, TA Instruments, manufactured by TA Instruments), and the mass reduction rate was measured. The outgassing property was evaluated as follows. A: The quality reduction rate is less than 1% B: The quality reduction rate is 1% or more, less than 5% C: The quality reduction rate is 5% or more

[Table 8]

[Table 9]

As is clear from the above table, in the production method of the present invention, a cured film excellent in corrosion resistance and chemical resistance can be obtained. In particular, by setting the temperature rise temperature during heating to a predetermined range, a cured film having various properties is more excellent.

<Example 100> The photosensitive resin composition of Example 11 was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then spin-coated (3,500 rpm, 30 seconds) to a resin having a thin copper layer formed thereon. Apply on the substrate. The photosensitive resin composition applied to the resin substrate was dried at 100 ° C for 5 minutes, and then exposed using an aligner (Karl-Suss MA150). Exposure was performed using a high pressure mercury lamp to measure the exposure energy at a wavelength of 365 nm. After exposure, the image was developed with cyclopentanone for 75 seconds. Then, heating was carried out at 180 ° C for 20 minutes. Thus, an interlayer insulating film for a rewiring layer is formed. The interlayer insulating film for a rewiring layer is excellent in insulation properties. In addition, the semiconductor element was produced using the interlayer insulating film for a rewiring layer, and as a result, it was confirmed that the operation was performed without any problem.

100‧‧‧Semiconductor components
101‧‧‧Layer
101a～101d‧‧‧ semiconductor devices
102b～102d‧‧‧through electrode
103a～103e‧‧‧Metal bumps
105‧‧‧Rewiring layer
110, 110a, 110b‧‧‧ underfill layer
115‧‧‧Insulation
120‧‧‧Wiring substrate
120a‧‧‧ surface electrode

Fig. 1 is a schematic view showing a configuration of an embodiment of a semiconductor device.

100‧‧‧Semiconductor components

101‧‧‧Layer

101a~101d‧‧‧ semiconductor devices

102b~102d‧‧‧through electrode

103a~103e‧‧‧Metal bumps

105‧‧‧Rewiring layer

110, 110a, 110b‧‧‧ underfill layer

115‧‧‧Insulation

120‧‧‧Wiring substrate

120a‧‧‧ surface electrode

Claims (18)

A method for producing a cured film, comprising: performing a layer comprising a composition comprising at least one of a polybenzazole precursor and a polybenzoxazole precursor and an amine generator at a temperature at a maximum heating temperature of 250 ° C or lower Heating, the amine content of the cured film is from 50 ppm to 5,000 ppm. The method for producing a cured film according to claim 1, wherein the amine generator is at least one of a photoamine generator and a hot amine generator. The method for producing a cured film according to the above aspect, wherein the amine generating agent is a hot amine generating agent. The method for producing a cured film according to the above aspect, wherein the composition does not contain an amine having a pKa8 or higher of a conjugate acid. The method for producing a cured film according to the first or second aspect of the invention, wherein the temperature is from 1 ° C / min to 10 ° C / min from a temperature of from 20 ° C to 150 ° C to the maximum heating temperature. The heating. The method for producing a cured film according to claim 5, wherein the heating is performed at the temperature increase rate, and after reaching a maximum heating temperature, heating is performed for 60 minutes to 240 minutes. The method for producing a cured film according to the first or second aspect of the invention, wherein the composition is 0.01% by mass based on the total amount of the polyimide intermediate and the polybenzoxazole precursor. The ratio of 45 mass% contains the amine generator. The method for producing a cured film according to claim 1 or 2, wherein the polyimine precursor is represented by the following general formula (2), and the polybenzoxazole precursor is General formula (3) represents; general formula (2) In the formula (2), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom. Or a monovalent organic group; general formula (3) In the formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ each independently represent a hydrogen atom or a monovalent organic group. The method for producing a cured film according to claim 8, wherein in the formula (2), at least one of A ¹ and A ² is an oxygen atom, and among the R ¹¹³ and R ¹¹⁴ , the adjacent A R ¹¹³ and R ^{114 in which 1} and A ² are an oxygen atom represent a monovalent organic group; or in the formula (3), R ¹²¹ is a linear aliphatic group. The method for producing a cured film according to the first or second aspect of the invention, wherein the maximum heating temperature is from 160 ° C to 250 ° C. The method for producing a cured film according to the above aspect, wherein the cured film has an amine content of from 500 ppm to 2,000 ppm. The method for producing a cured film according to the above aspect, wherein the composition further comprises a crosslinking agent. The method for producing a cured film according to claim 12, wherein the crosslinking agent has a molecular weight of from 100 to 800. The method for producing a cured film according to the above aspect, wherein the amine generator is selected from the group consisting of an acidic compound which generates an amine when heated to 40 ° C to 250 ° C, and has a pKa1 of 0 to 4. At least one of an anion and an ammonium salt of an ammonium cation. The method for producing a cured film according to claim 14, wherein the acidic compound is a compound which generates an amine when heated to 40 ° C to 250 ° C. The method for producing a cured film according to claim 14, wherein the acidic compound is a salt of an ammonium cation and a carboxylate anion. A method for producing an interlayer insulating film for a rewiring layer, which comprises the method for producing a cured film according to any one of claims 1 to 16. A method of producing a semiconductor device, comprising the method for producing a cured film according to any one of claims 1 to 16.