TW201600564A - Thermosetting resin composition, cured film, manufacturing method for cured film, and semiconductor device - Google Patents

Abstract

Provided are: a thermosetting resin composition with which the cyclization reaction of the thermosetting resin can be performed at low temperature and which has excellent stability; a cured film using said thermosetting resin composition; a manufacturing method for the cured film; and a semiconductor device. The thermosetting resin composition comprises a compound represented by general formula (1) and a thermosetting resin, which is cured by cyclization. In general formula (1), A represents a p-valent organic group, L1 represents an (m+1)-valent connecting group, L2 represents a (n+1)-valent connecting group, m represents an integer of at least 1, n represents an integer of at least 1, and p represents an integer of at least 1.

Description

Thermosetting resin composition, cured film, method for producing cured film, and semiconductor device

The present invention relates to a thermosetting resin composition, a cured film, a method for producing a cured film, and a semiconductor element. Specifically, the present invention relates to a thermosetting resin composition which can be preferably used for forming an insulating layer of a semiconductor element, a cured film using the thermosetting resin composition, a method for producing a cured film, and a method for producing a cured film. Semiconductor component.

The thermosetting resin which is cyclized and hardened by polyimine resin, polyamidoximine resin, or polybenzoxazole resin is excellent in heat resistance and insulation, and is used for an insulating layer of a semiconductor element. . Further, since the thermosetting resin has low solubility to a solvent, the precursor resin before the cyclization reaction (polyimine precursor resin, polyamidamine precursor resin, polybenzoxazole) The state of the precursor resin is used, and after being applied to a substrate or the like, heating is performed to cyclize the thermosetting resin to form a cured film.

For example, Patent Document 1 and Patent Document 2 disclose a composition comprising a polyimide intermediate precursor resin having a radical polymerizable group and a photopolymerization initiator. Patent Document 3 discloses a composition of an ester of a polydecylamine containing an ester group containing a photopolymerizable olefin double bond. Patent Document 4 discloses a composition comprising a polyimine precursor resin and a compound which generates a basic substance by radiation. Patent Document 5 discloses a photosensitive resin composition containing an N-aromatic glycine derivative and a polymer precursor. Patent Document 6 discloses a polyimine precursor resin composition comprising: a polyimide precursor; a thermal base generator comprising thermally decomposing and generating by heating at a temperature of 200 ° C or lower. a neutral compound of a secondary amine; and a solvent.

On the other hand, Patent Document 7 discloses a lithographic printing plate precursor having an image forming layer containing an infrared absorbing agent, a polymerization initiator, a polymerizable compound, a hydrophobic binder, and N- Phenylimidodiacetic acid. Further, Patent Document 8 discloses a laser-decomposable resin composition containing N-phenyliminodiacetic acid and a binder polymer. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. 2008-63553

[Problems to be solved by the invention]

A thermosetting resin which is cyclized and hardened by an alkali such as a polyimide, a polyimide, a polybenzazole precursor resin or a polybenzoxazole precursor resin can form a cured film excellent in heat resistance. However, heat treatment at a high temperature is required in the cyclization reaction of these thermosetting resins. Therefore, when the insulating layer or the like of the semiconductor element is formed by using such a thermosetting resin, there is a possibility that the heat of the cyclization reaction of the thermosetting resin causes thermal damage to the electronic component or the like, and the cyclization temperature is required. Further reduction.

The present inventors have studied the compositions disclosed in Patent Literatures 1 to 4, and as a result, it has been found that the temperature of the cyclization reaction of the thermosetting resin is high, and the curability at low temperatures is not sufficient.

Further, in Patent Document 5, as described in the paragraph No. 0014, it is an invention for the purpose of providing a photosensitive resin composition which can be obtained regardless of the type of the polyimide precursor resin. The solubility contrast, as a result, maintains a sufficient range of processes and obtains a well-shaped pattern, and for this purpose, an N-aromatic glycine derivative is used as a photobase generator. In other words, in Patent Document 5, an amine produced by irradiating light to an N-aromatic glycine derivative is used as a catalyst to carry out oxime imidization of a polyimide precursor resin, thereby curing the exposed portion. On the other hand, the difference in solubility between the exposed portion and the unexposed portion is imparted. However, in Patent Document 5, the study of lowering the cyclization temperature was not carried out, and in the examples, the ruthenium imidization was carried out by heating at 300 ° C for 1 hour.

Further, in Patent Document 6, a hot base generator containing a neutral compound which causes thermal decomposition by heating at a temperature of 200 ° C or lower and generates a secondary amine is used, but according to studies by the present inventors, it is known that the hot base The generating agent is in an equilibrium state of dissociation and non-dissociation in the composition. Therefore, it can be seen that during the storage of the composition, the polyamidene precursor resin undergoes a cyclization reaction, which tends to cause gelation or the like, and has poor stability.

On the other hand, Patent Document 7 and Patent Document 8 disclose an image forming layer or a laser decomposable resin composition using a carboxylic acid compound such as N-phenyliminodiacetic acid as a lithographic printing plate precursor. However, there is no description or suggestion that the cyclization temperature of the thermosetting resin is lowered.

Therefore, an object of the present invention is to provide a thermosetting resin composition which can be subjected to a cyclization reaction of a thermosetting resin at a low temperature and which is excellent in stability, a cured film using the thermosetting resin composition, and a cured film. Method and semiconductor component. [Means for solving the problem]

As a result of a detailed study, the present inventors have found that cyclization of a thermosetting resin can be provided by using a compound represented by the following formula (1) in combination with a thermosetting resin which is cyclized and cured by a base. The present invention has been completed by a thermosetting resin composition having a low temperature and excellent stability. The present invention provides the following. <1> A thermosetting resin composition comprising a compound represented by the following formula (1) and a thermosetting resin which is cyclized and cured by a base; [Chemical Formula 1] In the formula (1), A 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. <2> The thermosetting resin composition according to <1>, wherein in the formula (1), A is an aromatic ring group. <3> The thermosetting resin composition according to <1> or <2>, wherein in the formula (1), A is a benzene ring. The thermosetting resin composition as described in any one of <1>, wherein, in the formula (1), L ¹ and L ² are each independently an alkylene group. The thermosetting resin composition as described in any one of <1> to <4>, wherein m, n and p are each in the formula (1). The thermosetting resin composition as described in any one of <1>, wherein the compound represented by the formula (1) is N-aryliminodiacetic acid. The thermosetting resin composition according to any one of <1> to <6> wherein the thermosetting resin is selected from the group consisting of a polyimide precursor resin and a polyamidoximine precursor resin. And at least one of the polybenzoxazole precursor resins. The thermosetting resin composition according to any one of the above aspects, wherein the thermosetting resin has an ethylenically unsaturated bond. The thermosetting resin composition according to any one of <1> to <8>, further comprising a compound having an ethylenically unsaturated bond as a polymerizable compound. <10> The thermosetting resin composition according to <8> or <9>, which further comprises a photopolymerization initiator. <11> A cured film obtained by curing the thermosetting resin composition according to any one of <1> to <10>. <12> The cured film according to <11>, which is an interlayer insulating film for rewiring. <13> A method for producing a cured film, comprising: applying the thermosetting resin composition according to any one of <1> to <10> to a substrate, and correspondingly applying heat to the substrate The step of hardening the curable resin composition. <14> A semiconductor element comprising the cured film according to <11> or a cured film produced by the method according to <13>. <15> A hot base generator which is a compound represented by the following formula (1); In the formula (1), A 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. <16> The thermal base generator according to <15>, wherein in the formula (1), A is an aromatic ring group. <17> The hot base generator according to <15> or <16>, wherein in the formula (1), A is a benzene ring. The hot base generator according to any one of <15>, wherein, in the formula (1), L ¹ and L ² are each independently an alkylene group. The thermal base generator according to any one of <15>, wherein m, n and p are each in the formula (1). The hot base generator according to any one of <15>, wherein the compound represented by the formula (1) is N-aryliminodiacetic acid. [Effects of the Invention]

According to the present invention, it is possible to provide a thermosetting resin composition which can be subjected to a cyclization reaction of a thermosetting resin at a low temperature and has excellent stability, a cured film using the thermosetting resin composition, a method for producing a cured film, and a method for producing a cured film. Semiconductor component.

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 the present specification includes exposure using a mercury lamp, a far-ultraviolet light represented by a pseudo-molecular laser, X-rays, EUV light, or the like, and is performed by 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, the weight average molecular weight is defined as a polystyrene-converted value obtained by gel permeation chromatography (GPC). In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, by using HLC-8220 (manufactured by Tosoh), and TSKgel Super AWM-H (Dongcao (share) ) Manufactured, 6.0 mm inner diameter (Inner Diameter, ID) × 15.0 cm) was used as a pipe string. Unless otherwise specified, the solution was measured using a 10 mmol/L lithium bromide N-methylpyrrolidinone (NMP) solution.

<Thermosetting Resin Composition> The thermosetting resin composition of the present invention includes a compound represented by the formula (1) and a thermosetting resin which is cyclized with a base and which is hardened to be accelerated. According to the thermosetting resin composition of the present invention, the cyclization reaction of the thermosetting resin can be carried out at a low temperature, and a thermosetting resin composition excellent in stability can be obtained. It is speculated that this effect is based on the following reasons. In other words, the compound represented by the formula (1) is acidic at room temperature, but disappears by heating, carboxy decarbonation or dehydration cyclization, whereby the amine moiety which has been previously neutralized and neutralized becomes active. Become alkaline. Further, it is considered that the cyclization reaction of the thermosetting resin is promoted by the base produced by the compound represented by the free formula (1). In addition, as described above, the compound represented by the formula (1) is acidic at room temperature, so that the cyclization reaction of the thermosetting resin cannot be promoted. Therefore, even if the compound represented by the formula (1) is stored in a state of being mixed with a thermosetting resin which is cyclized by a base and which is hardened to be accelerated, the reaction is not carried out unless it is heated, so that it is preferred. . The invention is described in detail below.

<<Compound represented by the formula (1)>> The thermosetting resin composition of the present invention includes the compound represented by the formula (1). This compound is a compound which functions as a hot base generator by generating a base by heating. It is usually present as an acidic compound before heating. 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. And stirred at room temperature for 1 hour. The value of the solution measured at 20 ° C was less than 7 using a pH meter.

[Chemical 3] In the formula (1), A 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, and p represents an integer of 1 or more

In the formula (1), A represents a p-valent organic group. The organic group may, for example, be an aliphatic group or an aromatic ring group, and is preferably an aromatic ring group. By setting A as an aromatic ring group, a base having a high boiling point can be easily produced at a lower temperature. By increasing the boiling point of the alkali to be produced, it is difficult to volatilize or decompose due to heating during curing of the thermosetting resin, and cyclization of the thermosetting resin can be performed more efficiently. Examples of the monovalent aliphatic group include an alkyl group, a cycloalkyl 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 either a straight chain or a branched one. 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, and a dodecyl group. The carbon number of the cycloalkyl group is preferably from 3 to 30, more preferably from 3 to 20, still more preferably from 3 to 10. The cycloalkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include 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 either a straight chain or a branched 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. The divalent or higher aliphatic group may be a group obtained by removing one or more hydrogen atoms from the monovalent aliphatic group. The aromatic ring group may be a single ring or a polycyclic ring. The aromatic ring group may also be a heteroaromatic ring group containing a hetero atom. The aromatic ring group may have a substituent or may be unsubstituted. It is preferably unsubstituted. Specific examples of the aromatic ring group include a benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, an indecene ring, an anthracene ring, and a thick ring. Pentabenzene ring, terpene ring, phenanthrene ring, anthracene ring, thick tetraphenyl ring, Chrysene ring, triphenylene ring, anthracene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring , pyridazine ring, anthracene ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazoline ring, quinoline ring, pyridazine ring, naphthyridine ring, quinoxaline ring , quinoxaline ring, isoquinoline ring, carbazole ring, pyridine ring, acridine ring, phenanthroline ring, thioxan ring, chromene ring, dibenzopyran ring, morphine The ring, the phenothiazine ring, and the phenazine ring are preferably benzene rings. The aromatic ring group may also be bonded to a plurality of aromatic rings via a single bond or a linking group to be described later. As the linking group, for example, an alkyl group is preferred. It is also preferred that the alkyl group is linear or branched. Specific examples of the aromatic ring group in which a plurality of aromatic rings are bonded via a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, and triphenylmethane. Tetraphenylmethane and the like.

Examples of the substituent which the organic group represented by A may include, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; or an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group; An aryloxy 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 oxime group such as an ethyl fluorenyl group, a benzamidine group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group, and a methoxycyanyl group; an alkyl fluorenyl group such as a methyl fluorenyl group and a tert-butyl fluorenyl group; An aryl fluorenyl group such as a phenyl fluorenyl group and a p-tolyl fluorenyl group; an alkyl group such as a methyl group, an ethyl group, a tert-butyl group or a dodecyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or an adamantyl group; An aryl group such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl and phenanthryl; hydroxy; carboxy; indenyl; sulfo; cyano; alkylaminocarbonyl; arylamine Alkylcarbonyl; sulfonylamino; decylalkyl; amine; monoalkylamine; dialkylamine; arylamine; and diarylaminothiol; or combination.

L ¹ represents a (m+1)-valent linking group, and L ² represents a (n+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 straight carbon number of 1 to 10) A chain extending alkenyl group or a branched chain extending alkenyl group) or 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, and particularly preferably methylene.

m and n represent an integer of 1 or more, preferably 1 or 2, more preferably 1. The upper limit of m and n is the maximum number of substituents which can be used for the linking group represented by L ¹ and L ² . When m and n are 1, heating of 200 ° C or lower is likely to cause a tertiary amine having a high boiling point. Further, the stability of the thermosetting resin 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 can be employed for the organic group represented by A. When p is 1, heating at 200 ° C or lower is likely to cause a tertiary amine having a high boiling point.

The compound represented by the formula (1) is preferably N-aryliminodiacetic acid. N-aryliminodiacetic acid is a compound in which A in the formula (1) is an aromatic ring group, L ¹ and L ² are methylene groups, m is 1, n is 1, and p is 1. The N-aryliminodiacetic acid is easily heated to a tertiary amine having a high boiling point by heating at 200 ° C or lower.

The compound represented by the formula (1) is preferably a compound which generates a base when heated to 120 ° C to 230 ° C, more preferably a compound which generates a base at 120 ° C to 200 ° C. The alkali generation temperature can be measured, for example, by differential scanning calorimetry, and the compound is heated to 250 ° C at 5 ° C / min in a pressure resistant capsule, and the peak temperature of the heat generation peak having the lowest temperature is read, and the peak temperature is taken as the alkali generation temperature. The measurement was carried out. The base produced by the compound represented by the formula (1) 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 thermosetting resin can be further lowered. The boiling point of the base produced by the compound represented by the formula (1) 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 base is preferably from 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is preferably 500 or less. Further, the value of the molecular weight is a theoretical value obtained from the structural formula.

Specific examples of the compound represented by the formula (1) 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. Further, Me in the following formula represents a methyl group. Among the compounds shown below, preferred are (A-1) to (A-9), (A-13) to (A-17), (A-19), (A-20), and more preferably (A-1), (A-2), (A-3), (A-4), (A-8), (A-9), (A-19).

[Chemical 4]

The content of the compound represented by the formula (1) is preferably from 0.1% by mass to 50% by mass based on the total solid content of the thermosetting resin composition of the present invention. 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. When the content of the compound represented by the formula (1) is in the above range, the thermosetting resin can be cyclized at a low temperature, and a cured film excellent in heat resistance can be formed by heat treatment at a low temperature. The thermosetting resin composition of the present invention preferably contains the compound represented by the formula (1) in an amount of 0.1 part by mass to 30 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the thermosetting resin. 20 parts by mass. The compound represented by the formula (1) 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.

<<Thermosetting Resin Resin>> The thermosetting resin composition of the present invention includes a thermosetting resin which is cyclized by an alkali and which is hardened to be accelerated. The thermosetting resin is preferably a heterocyclic-containing polymer precursor resin which generates a cyclization reaction by heating and forms a heterocyclic-containing polymer. The polymer precursor resin containing a hetero ring is preferably one or more selected from the group consisting of a polyimine precursor resin, a polyamidoximine precursor resin, and a polybenzoxazole precursor resin, more preferably It is a polyimine precursor resin or a polybenzoxazole precursor resin, and more preferably a polyimine precursor resin. According to this aspect, it is easy to form a cured film which is more excellent in heat resistance. Further, these thermosetting resins have a high cyclization temperature and are previously heated to 300 ° C or higher for cyclization. However, according to the present invention, even those thermosetting resins may be used at 300 ° C or lower (preferably The cyclization reaction is sufficiently carried out by heating at 200 ° C or lower, more preferably 180 ° C or lower, whereby the effects of the present invention can be more remarkably obtained. In the present invention, the thermosetting resin preferably has an ethylenically unsaturated bond, more preferably a polyimide precursor resin having an ethylenically unsaturated bond. When the thermosetting resin has an ethylenically unsaturated bond, it is easy to form a cured film having more excellent heat resistance. Further, when patterning is performed by photolithography, the sensitivity can be improved. The content of the thermosetting resin in the thermosetting resin composition of the present invention is preferably from 30% by mass to 90% by mass based on the total solid content of the thermosetting resin composition. The lower limit is more preferably 40% by mass or more, and still more preferably 50% by mass or more.

<<<Polyimide precursor resin, polyamidamine precursor resin>>> The polyimine precursor resin is not particularly limited as long as it is a compound which can be polyimidized. However, a polyimine precursor resin having an ethylenically unsaturated bond is preferred. Further, the polyamidoximine precursor resin is not particularly limited as long as it is a compound which can be imidized by polyamidoxime, but is preferably a polyamidoximine precursor having an ethylenically unsaturated bond. Resin. The polyimine precursor resin and the polyamidoximine precursor resin are preferably compounds containing a repeating unit represented by the following formula (2).

[Chemical 5] 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 ¹¹² represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are each independently represented. A hydrogen atom or a monovalent organic group.

A ¹ and A ² each independently represent an oxygen atom or -NH-, preferably an oxygen atom.

R ¹¹¹ represents a divalent organic group. The divalent organic group may, for example, be a diamine residue remaining after the removal of the amine group of the diamine. Examples of the diamine include an aliphatic diamine, a cyclic aliphatic diamine, and an 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 isophorone II Amine; 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-amine Phenylphenyl)hexafluoropropane, 4,4'-diamino-p-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'-dimethyl-4,4'-diaminodiphenylanthracene, 1,3-double (4-Aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenyl)benzene, bis[4-(4-amine Phenyloxy)]phenyl ether, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenyl Methane, 4,4'-diamino octafluorobiphenyl, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amine Phenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroquinone, 3, 3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminopurine, 1,5-diaminoguanidine , bis[4-(4-aminophenoxy)phenyl]indole, bis[4-(3-aminophenoxy) Phenyl] anthracene, bis[4-(2-aminophenoxy)phenyl]anthracene, 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'-di Aminodiphenylmethane, 2,4-diaminocumene and 2,5-diaminocumene, 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-diamine Base, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzilide, ester of diaminobenzoic acid, 1,5-diamine Naphthalene, diaminotrifluorotoluene, diaminoguanidine, 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-amine Phenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminobenzene) Oxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl] Hexafluoropropane, pair (4-Amino-2-trifluoromethylphenoxy)benzene, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl, 4,4'-bis ( 4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4'-bis(4-amino-2-trifluoromethylphenoxy)diphenylanthracene, 4,4'- Bis(3-amino-5-trifluoromethylphenoxy)diphenylphosphonium, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexa Fluoropropane, 3,3',5,5'-tetramethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2 a diamine residue remaining after removal of an amine group of at least one diamine of 2', 5, 5', 6, 6'-hexafluorotoluidine and 4,4'''-diaminotetrabiphenyl base.

R ¹¹² represents a tetravalent organic group. Examples of the tetravalent organic group 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. From pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic acid Dihydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4, 4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride , 2,3,3',4'-benzophenone tetracarboxylic dianhydride, dianhydride of oxydiphthalic acid, 3,3',4,4'-diphenyl oxide tetracarboxylic acid Dihydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 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-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1- Bis(3,4-dicarboxybenzene Ethylene dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one of the C1-C6 alkyl derivatives and the C1-C6 alkoxy derivatives The tetracarboxylic acid residue remaining after the anhydride group is removed from the anhydride.

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 of 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 the aryl carbon. 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 a HO group. When R ¹¹³ and R ¹¹⁴ are a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group, and a 4-hydroxybenzyl group, the solubility in an aqueous developing solution is good, and it can be suitably used as a negative-type thermosetting resin. Composition.

From the viewpoint of the solubility of the organic solvent, R ¹¹³ and R ^{114 are} preferably a monovalent organic group. As the monovalent organic group, an alkyl group, a cycloalkyl group or an aromatic ring group is particularly preferred. Specific examples of the alkyl group are preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof 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, and a decyl group. Anthracenyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, tbutyl, tert-butyl, 1-ethylpentyl, and 2-ethylhexyl. The cycloalkyl group may specifically be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl 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 cycloalkyl group include adamantyl group, norbornyl group, borneol group, campphenyl group, decahydronaphthyl group, tricyclodecyl group, tetracyclodecyl group, and fluorene group. Base, dicyclohexyl and pinenyl. Among them, from the viewpoint of coexistence with high sensitivity, the cyclohexyl group is most preferable. The aromatic ring group is specifically a substituted or unsubstituted benzene ring, a naphthalene ring, a pentylene ring, an anthracene ring, an anthracene ring, a heptene ring, a dicyclopentadienyl ring, or an anthracene. Ring, fused pentene ring, terpene 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, chromene ring, dibenzopyran ring, morphine ring, phenothiazine ring or phenazine ring. The best is the benzene ring.

In the formula (2), at least one of R ¹¹³ and R ¹¹⁴ preferably represents a polymerizable group. Thereby, the sensitivity and the resolution can be made better.

Examples of the polymerizable group represented by R ¹¹³ and R ¹¹⁴ 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. Base. 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).

[Chemical 6]

In the formula (III), R ²⁰⁰ represents hydrogen 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. , octamethyl, dodecamethylene, -CH ₂ CH(OH)CH ₂ -, more 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.

The ratio of R ¹¹³ and R ¹¹⁴ in the formula (2) to a polymerizable group is in terms of a molar ratio, and the polymerizable group: the non-polymerizable group is preferably 100:0 to 5:95, more preferably 100:0. 20:80, the best is 100:0 to 50:50.

The polyimine precursor resin and the polyamidamine precursor resin may contain, in addition to the repeating structural unit of the above formula (2) based on a single R ¹¹¹ or R ¹¹² , More than 2 different types of repeating units. Further, the polyimine precursor resin and the polyamidamine precursor resin may contain repeating units which are structural isomers. The expression of the structural isomer pair as a unit of the formula (2), for example, the following is an example of a unit of the formula (2) in which R ¹¹² derived from pyromellitic acid is represented by a pyromellitic acid residue (A) ¹ and A ² =-O-). Further, in addition to the repeating unit of the above formula (2), the polyimine precursor resin and the polyamidamine precursor resin may contain other kinds of repeating structural units.

[Chemistry 7]

The weight average molecular weight (Mw) of the polyimine precursor resin and the polyamidamine precursor resin is preferably from 1,000 to 100,000, more preferably from 3,000 to 50,000, most preferably from 5,000 to 30,000. The weight average molecular weight (Mw) of the polyimine precursor resin and the polyamidamine precursor resin can be measured, for example, by gel filtration chromatography corrected by polystyrene.

<<<Polybenzoxazole precursor resin>>> The polybenzoxazole precursor resin is not particularly limited as long as it is a polybenzoxazole-based compound, but is preferably ethylenic. A polybenzoxazole precursor resin with an unsaturated bond. In particular, it is preferably a compound represented by the following formula (3).

[化8] 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. As the divalent organic group, an aromatic ring group is preferred. Examples of the aromatic ring group include the following.

[Chemistry 9] Wherein A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ - Base.

R ¹²² represents a tetravalent organic group. The tetravalent organic group is preferably a residue of a bisaminophenol represented by the following formula (A). Ar(NH ₂ ) ₂ (OH) ₂ (A) wherein Ar is an aryl group.

As the bisphenol of the above formula (A), for example, 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'- Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 4,4'-diamino-3,3'-di Hydroxydiphenyl hydrazine, 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-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamine 4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxy Diphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxy Benzene, etc. These bisaminophenols may be used singly or in combination.

Among the bisaminophenols represented by the formula (A), a bisaminophenol having an aromatic ring group selected from the group consisting of the following is particularly preferred.

[化10] 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 formula (A) are bonded to each other in the ortho position (adjacent position).

R ¹²³ and R ¹²⁴ represent a hydrogen atom or a monovalent organic group, and preferably at least one of R ¹²³ and R ¹²⁴ represents a polymerizable group. As the polymerizable group, the forms described in R ¹¹³ and R ^{114 of the} above formula (2) are the same, and the preferred ranges are also the same.

In addition to the repeating unit of the above formula (3), the polybenzoxazole precursor resin may contain other kinds of repeating structural units.

The polybenzoxazole precursor resin preferably has a weight average molecular weight (Mw) of from 1,000 to 100,000, more preferably from 3,000 to 50,000, particularly preferably from 5,000 to 30,000. The weight average molecular weight (Mw) of the polybenzoxazole precursor resin can be measured, for example, by gel filtration chromatography corrected by polystyrene.

<<Polymerizable Compound>> The thermosetting resin composition of the present invention may contain the compound represented by the formula (1) and a polymerizable compound other than the thermosetting resin. By containing a polymerizable compound, a cured film having more excellent heat resistance can be formed. Further, pattern formation can also be performed by photolithography. The polymerizable compound is a compound having a polymerizable group, and a known compound which can be polymerized by a radical can be used. The polymerizable group is a group which can be polymerized by the action of actinic rays, radiation, or radicals, and examples thereof include a group having an ethylenically unsaturated bond. The group having an ethylenically unsaturated bond is preferably a styryl group, a vinyl group, a (meth)acryl fluorenyl group or a (meth)allyl group, more preferably a (meth) acrylonitrile group. That is, the polymerizable compound used in the present invention is preferably a compound having an ethylenically unsaturated bond, more preferably a (meth) acrylate compound, and still more preferably an acrylate compound. The polymerizable compound is widely known in the industrial field, and the polymerizable compound can be used without particular limitation in the present invention. These polymerizable compounds may be, for example, any of a chemical form such as a monomer, a prepolymer, an oligomer, or a mixture thereof, and a polymer of the above.

In the present invention, the monomeric polymerizable compound (hereinafter also referred to as a polymerizable monomer) is a compound different from the polymer compound. The polymerizable 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 polymerizable monomer is usually 100 or more. Further, the oligomeric polymerizable compound (hereinafter also referred to as a polymerizable oligomer) is typically a polymer having a relatively low molecular weight, preferably a polymer of 10 to 100 polymerizable monomers. Things. The polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC) is preferably from 2,000 to 20,000, more preferably from 2,000 to 15,000, most preferably from 2,000 to 10,000.

The number of functional groups of the polymerizable compound in the present invention means the number of polymerizable groups in one molecule. The polymerizable compound is preferably a difunctional or higher polymerizable compound containing at least one polymerizable group, and more preferably contains at least one trifunctional or higher polymerizable compound. In addition, the polymerizable compound in the present invention preferably contains at least one trifunctional or higher polymerizable compound from the viewpoint of forming a three-dimensional crosslinked structure and improving heat resistance. Further, it may be a mixture of a difunctional or less polymerizable compound and a trifunctional or higher polymerizable compound.

Specific examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, guanamines, and These polymers are preferably esters of an unsaturated carboxylic acid and a polyol compound, and amides of an unsaturated carboxylic acid and a polyamine compound, and a multimer of these. Further, an unsaturated carboxylic acid ester or a guanamine having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group, an addition reaction with a monofunctional or polyfunctional isocyanate or an epoxy group, or A dehydration condensation reaction with a monofunctional or polyfunctional carboxylic acid or the like. Further, an addition reaction product of an unsaturated carboxylic acid ester or an oxime amine having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, an amine or a thiol, A substituted carboxylic acid ester such as a halogen group or a toluenesulfonyloxy group or a decylamine and a substituted reactant of a monofunctional or polyfunctional alcohol, an amine or a thiol are 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-Methoxypropenyloxy-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 JP-A-46-27926, JP-A-51-47334, and JP-A-57-196231 can be suitably used. Japanese Patent Laid-Open No. Hei 59-5240, Japanese Patent Laid-Open No. Hei 59-5241, and Japanese Patent Laid-Open No. Hei 2-226149 The amine group or the like described in the publication.

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.

Examples of other preferable amide-based monomers include those having a cyclohexylene structure described in Japanese Patent Publication No. Sho 54-21726.

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 the polyisocyanate compound having two or more isocyanate groups in one molecule, two or more polymerizable groups are contained in one molecule obtained by adding a hydroxyl group-containing vinyl monomer represented by the following formula (A). A vinyl vinyl urethane compound or the like. CH ₂ =C(R ⁴ )COOCH ₂ CH(R ⁵ )OH· (A) (wherein R ⁴ and R ⁵ represent H or CH ₃ ) Further, as disclosed in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Publication No. 2-32293, Japanese Patent Publication No. Hei 2-16765, or Japanese Patent Publication No. Sho-58-49860, Japanese Patent Publication No. SHO-58-17654 A urethane compound having an ethylene oxide-based skeleton described in Japanese Patent Publication No. Sho 62-39417, and Japanese Patent Publication No. Sho 62-39418 is also suitable.

Further, in the present invention, as the polymerizable compound, a compound described in Paragraph No. 0095 to Paragraph No. 0108 of JP-A-2009-288705 can be suitably used.

Further, as the polymerizable compound, a compound having a boiling point of 100 ° C or higher at normal pressure is also preferable. Examples thereof include monofunctional acrylates or 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 urethane described in Japanese Patent Publication No. Sho-48-41708, the Japanese Patent Publication No. SHO-50-63193, and the Japanese Patent Publication No. Sho 51-37193 Japanese Patent Publication No. Sho 48-64183, Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho 52-3 The polyester acrylate described in the publication No. 0490, a polyfunctional acrylate or methacrylate such as an epoxy acrylate which is a reaction product of an epoxy resin and (meth)acrylic acid, and a mixture thereof. 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 the other preferable polymerizable compound, an anthracene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and Japanese Patent No. 4,364,216, and the like can be used. A compound of two or more groups containing an ethylenically unsaturated bond, a cardo resin. Further, as another example of the polymerizable compound, a specific unsaturated compound described in JP-A-46-43946, JP-A-1-40337, and JP-A No. 1-40336, A vinylphosphonic acid-based compound or the like described in JP-A No. 2-25493. Further, in some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is suitably used. Further, it can also be used as a photocurable monomer and oligomer in "Japan Next Association" Vol. 20, No. 7, 300 pages to 308 (1984).

In addition to the above, a polymerizable compound 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.

[11]

[化12]

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 above formula (MO-1) to 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 polymerizable compound represented by the above formula (MO-1) to (MO-5), a paragraph of JP-A-2007-269779 may be suitably used. The compound described in No. 0248 to Paragraph No. 0251.

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 polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available as Kaya) are preferred. KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercial product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.) , dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and the (meth) propylene sulfhydryl groups of these are separated by ethylene glycol. The structure of the residue and the propylene glycol residue. These oligomer types can also be used.

The polymerizable compound may 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 hardenability is good.

As the polymerizable compound, a polymerizable compound having a caprolactone structure can also be used. The polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trishydroxymethylethane, di-trimethylolethane, and trishydroxyl. Polyols such as methyl propane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin, and trimethylol melamine are esterified with (meth)acrylic acid and ε-caprolactone to obtain The ε-caprolactone is modified with a polyfunctional (meth) acrylate. Among them, a polymerizable compound having a caprolactone structure represented by the following formula (B) is preferred.

General formula (B) [Chemical 13]

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

General formula (C) [Chemistry 14]

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

General formula (D) [Chem. 15]

(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 (B) to the formula In (D), m = 1, a compound represented by the formula (C) = 2, a compound in which R ¹ is a hydrogen atom), DPCA-30 (the above formula (B) to a formula (D) Wherein m = 1, a compound represented by the formula (C) = 3, a compound in which R ¹ is a hydrogen atom), and DPCA-60 (in the formula (B) to (D) , m = 1, a compound represented by the formula (C) = 6 and a compound in which R ¹ is a hydrogen atom), DPCA-120 (in the above formula (B) to (D), m =2, the number of the groups represented by the general formula (C) = 6, the compound in which R ¹ is a hydrogen atom) and the like. In the present invention, the polymerizable compound having a caprolactone structure may be used singly or in combination of two or more.

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

[Chemistry 16]

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 a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth)acryloyl chloride. 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/or 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17]

[化18]

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 the polymerizable compound, acrylic acid as described in Japanese Patent Publication No. Sho. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A urethane, or a ring as 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 of an oxyethylene skeleton 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 polymerizable compound include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), and NK ESTER M-40G. NK ester (NK ESTER) 4G, NK ester (NK ESTER) M-9300, NK ester (NK ESTER) A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha), Blemmer PME400 (manufactured by Nippon Oil Co., Ltd.), etc.

From the viewpoint of heat resistance, the polymerizable compound preferably has a partial structure represented by the following formula.

[Chemistry 19] The * in the formula is a link key.

Specific examples of the polymerizable compound having the partial structure include trimethylolpropane tri(meth)acrylate, isomeric cyanuric acid ethylene oxide modified di(meth)acrylate, and the like. Cyanuric acid ethylene oxide modified tris(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, two Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol methane tetra (meth) acrylate, etc., in the present invention, these polymerizable compounds can be particularly preferably used.

In the thermosetting resin composition of the present invention, the content of the polymerizable compound is preferably 1% by mass based on the total solid content of the thermosetting resin composition from the viewpoint of good curability and heat resistance. 50% by mass. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. The polymerizable compound may be used alone or in combination of two or more. Further, the mass ratio of the thermosetting resin to the polymerizable compound (thermosetting resin/polymerizable compound) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, most preferably 90/. 10 to 50/50. When the mass ratio of the thermosetting resin to the polymerizable compound is in the above range, a cured film having more excellent curability and heat resistance can be formed.

<<Thermal polymerization initiator>> The thermosetting resin composition of the present invention may further contain a thermal polymerization initiator. As the thermal polymerization initiator, a known thermal polymerization initiator can be used. The thermal 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 thermosetting resin is carried out by adding a thermal polymerization initiator, the polymerization reaction of the polymerizable compound can be carried out. In addition, when the thermosetting resin contains an ethylenically unsaturated bond, the cyclization of the thermosetting resin can be carried out together with the polymerization reaction of the thermosetting resin, so that higher heat resistance can be achieved. Examples of the thermal polymerization initiator include aromatic ketones, phosphonium salt compounds, organic peroxides, sulfur compounds, hexaarylbiimidazole compounds, ketoxime compounds, borate compounds, oxazine compounds, and metallocenes. A compound, an active ester compound, a compound having a carbon halogen bond, an azo compound, or the like. Among them, an organic peroxide or an azo compound is more preferred, and a peroxide is particularly preferred. Specifically, a compound described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be cited. Among the commercially available products, Perbutyl Z (manufactured by Nippon Oil Co., Ltd.) can be suitably used.

When the thermosetting resin composition of the present invention has a thermal polymerization initiator, the content of the thermal polymerization initiator is preferably from 0.1% by mass to 50% by mass based on the total solid content of the thermosetting resin composition. It is preferably from 0.1% by mass to 30% by mass, 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, per 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 polymerization initiator may be used alone or in combination of two or more. When the number of the thermal polymerization initiators is two or more, it is preferred that the total is in the above range.

<<Sensitizing dye>> The thermosetting resin composition of the present invention may further 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 a compound represented by the formula (1), a thermal polymerization initiator, a photopolymerization initiator, or the like to cause movement of electrons, energy movement, heat generation, and the like. Thereby, the compound represented by the formula (1), the thermal polymerization initiator, and the photopolymerization initiator are chemically changed to be decomposed to generate a radical, an acid or a base.

Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in a region of 300 nm to 450 nm. For example, polynuclear aromatics (for example, phenanthrene, anthracene, anthracene, anthracene, triphenylene, 9.10-dialkoxypurine), xanthenes (for example, luciferin, blush, red erythro, rose red B) , Bengal rose red), thioxanthone, cyanine (such as thiacarbocyanine, oxacarbocyanine), merocyanine (such as merocyanine, carbonyl chloroform), thiazide ( For example, thiazide, methylene blue, toluidine blue), acridines (such as acridine orange, chloroflavin, acridine flavin), guanidines (such as guanidine), squaraine guanidine salts (such as Acid ylide, coumarin (eg 7-diethylamino-4-methylcoumarin), phenothiazines, styrylbenzenes, distyrylbenzenes, Oxazoles and so on.

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

When the thermosetting resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass based on the total solid content of the thermosetting resin composition. From 5% to 15% by mass, more preferably from 0.5% by mass to 10% by mass. The sensitizing dye may be used alone or in combination of two or more.

<<Photopolymerization initiator>> The thermosetting resin composition of the invention may further contain a photopolymerization initiator. When the thermosetting resin composition of the present invention contains a photopolymerization initiator, a thermosetting resin composition is applied to a semiconductor wafer or the like to form a layered composition layer, and then light is irradiated, thereby generating radicals. The hardening by the acid can lower the solubility in the light-irradiating portion. 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 photopolymerization initiator is not particularly limited as long as it has a function of starting a polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, it is preferred that the ultraviolet region has a sensitivity to visible light. Alternatively, it may be an active agent that produces a reactive radical with a certain effect on the photoexcited sensitizer. The photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of from about 300 nm to 800 nm, preferably from 330 nm to 500 nm. The molar absorption coefficient of the compound can be measured by a known method, and specifically, for example, by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.), The measurement was carried out at a concentration of 0.01 g/L using an ethyl acetate solvent.

As a photopolymerization 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.), and a mercapto group. a mercaptophosphine compound such as a phosphine oxide, a ruthenium 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, or a hydroxybenzene Ethyl ketone, azo compound, azide compound, metallocene compound, organoboron compound, iron aromatic hydrocarbon complex, and the like.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include, for example, a compound described in Japanese Society of Chemical Society (Bull. Chem. Soc. Japan), 42, 2924 (1969), and the specification of British Patent No. 1,388,492. The compound described in Japanese Patent Laid-Open Publication No. SHO 53-133428, the compound described in the specification of German Patent No. 3337024, and the "J. Org. Chem." by FC Schaefer et al., 29 The compound described in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The compound or the like described in the specification of Patent No. 4212976.

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-(1-naphthyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(4-n-butoxystyrene Base)-1,3,4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).

Further, examples of the photopolymerization initiator other than the above include an acridine derivative (for example, 9-phenyl acridine, 1,7-bis(9,9'-acridinyl)heptane, etc.), N. -Phenylglycine, etc., polyhalogen compounds (for example, carbon tetrabromide, phenyltribromomethylhydrazine, phenyltrichloromethyl ketone, etc.), coumarins (for example, 3-(2-benzofuran) Mercapto)-7-diethylamino coumarin, 3-(2-benzofuranyl)-7-(1-pyrrolidinyl)coumarin, 3-benzylidene-7- Diethylamino coumarin, 3-(2-methoxybenzimidyl)-7-diethylamino coumarin, 3-(4-dimethylaminobenzimidyl)- 7-Diethylamino coumarin, 3,3'-carbonyl bis(5,7-di-n-propoxycoumarin), 3,3'-carbonyl bis(7-diethylamine scent Beans), 3-benzylidene-7-methoxycoumarin, 3-(2-furanyl)-7-diethylaminocoumarin, 3-(4-diethyl Amino cinnamonyl)-7-diethylamino coumarin, 7-methoxy-3-(3-pyridylcarbonyl)coumarin, 3-benzylidene-5,7-dipropyl Oxycoumarin, 7-benzotriazol-2-ylcoumarin, Japanese Patent Laid-Open No. Hei 5-19475, Japanese Patent Laid-Open No. Hei 7-27102 Cocoa beans as described in the publication No. JP-A-2002-363206, JP-A-2002-363207, JP-A-2002-363208, and JP-A-2002-363209 Ordinary compounds, etc., fluorenylphosphine oxides (for example, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)- 2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc., metallocenes (eg bis(η5-2,4-cyclopentadien-1-yl)- Bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, η5-cyclopentadienyl-η6- cumenyl-iron(1+)-hexafluorophosphate (1), etc., the compounds described in Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent Publication No. Sho 57-1819, Japanese Patent Publication No. Sho 57-6096, and U.S. Patent No. 3,615,455 Wait.

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, and 4-methoxybenzophenone. 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenone tetracarboxylic acid Or a tetramethyl ester thereof, 4,4'-bis(dialkylamino)benzophenone (for example, 4,4'-bis(dimethylamino)benzophenone, 4,4'-double (dicyclohexylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dihydroxyethylamino)benzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylamine Acetophenone, benzophenone, anthracene, 2-tert-butylhydrazine, 2-methylindole, phenanthrenequinone, xanthone, thioxanthone, 2-chloro-thiazinone, 2,4-Diethylthioxanthone, anthrone, 2-benzyl-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, 2-methyl-1- [4-(Methylthio)phenyl]-2-morpholinyl-1-propanone, 2-hydroxy-2-methyl-[4-(1-methylvinyl)phenyl]propanol oligomerization , benzoin, benzoin ethers (eg, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methyl Acridinone, N-butyl acridone, N-butyl-chloroacridone, etc. Among the commercially available products, Kayacure DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be suitably used.

As the photopolymerization 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. 42258899 can be used. . As a hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, Yanjia can be used. 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 wavelength of absorption of a long-wavelength source such as 365 nm or 405 nm, can 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.

More preferably, the photopolymerization initiator is an anthraquinone compound. As a specific example of the oxime-based initiator, 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.

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, and Japanese Patent The compound or the like described in each of the publications of Japanese Laid-Open Patent Publication No. JP-A-2006-342166. Commercially available products such as IRGACURE-OXE01 (manufactured by BASF Corporation), IRGACURE-OXE02 (manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA) are also suitably used.

In addition, the compound described in Japanese Patent Laid-Open Publication No. 2009-519904, which is bonded to the N-position of the carbazole, 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 Laid-Open Patent Publication No. 2010-15025, and the ketone oxime compound described in International Patent Publication No. 2009-131189, and the same. A compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Wait. 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 absorbing 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. The ruthenium compound having a specific substituent as shown in Japanese Laid-Open Patent Publication No. 2007-269779, or the bismuth group having a thioaryl group as shown in Japanese Laid-Open Patent Publication No. 2009-191061. Compounds, etc.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, and a mercapto group. Phosphine compound, phosphine oxide compound, metallocene compound, hydrazine compound, triallyl 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. , particularly preferably at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an anthraquinone compound, a triaryl imidazole dimer, and a benzophenone compound, preferably Use a hydrazine compound.

Further, as the photopolymerization initiator, a compound which produces an acid having a pKa of 4 or less is preferable, and a compound which produces an acid having a pKa of 3 or less is more preferable. Examples of the acid generating compound include trichloromethyl-s-triazine, sulfonium or phosphonium salt, quaternary ammonium salt, diazomethane compound, sulfhydryl sulfonate compound, and sulfonic acid. Ester compound and the like. Among these, an oxime sulfonate compound is preferably used from the viewpoint of high sensitivity. These acid generators may be used alone or in combination of two or more. Specifically, an acid generator described in paragraphs [0073] to [0095] of JP-A-2012-8223 is mentioned.

When the thermosetting resin composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably from 0.1% by mass to 30% by mass, more preferably 0.1%, based on the total solid content of the thermosetting resin composition. The mass% to 20% by mass, and more preferably 0.1% by mass to 10% by mass. In addition, it is preferably contained in an amount of from 1 part by mass to 20 parts by mass, more preferably from 3 parts by mass to 10 parts by mass, per 100 parts by mass of the polymerizable compound. The photopolymerization initiator may be used alone or in combination of two or more. When the amount of the photopolymerization initiator is two or more, it is preferred that the total is in the above range.

<<Chain Transfer Agent>> The thermosetting resin composition of the present invention may further contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Society for Polymerics, 2005) at pages 683-684. 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 thermosetting resin 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 100 parts by mass based on the total solid content of the thermosetting resin composition. It is particularly preferably 1 part by mass to 5 parts by mass, and is preferably 1 part by mass to 10 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 thermoplastic resin and a polymerizable compound during or during the production process, it is preferred to add a small amount of polymerization inhibition to the thermosetting resin composition of the present invention. Agent. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallic phenol, tert-butylcatechol, benzoquinone, 4, 4 can be suitably cited. '-Thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitroso- N-phenylhydroxylamine aluminum salt. When the thermosetting resin 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 thermosetting resin 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.

<<High-Fourty Fatty Acid Derivatives and the like>> In the thermosetting resin composition of the present invention, in order to prevent polymerization inhibition by oxygen, it is also possible to add a higher fatty acid derivative such as behenic acid or behenylamine. The substance or the like is biased to exist on the surface of the thermosetting resin composition during drying after coating. When the thermosetting resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably from 0.1% by mass to 10% by mass based on the total solid content of the thermosetting resin 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 thermosetting resin composition of the present invention is layered by coating, it is preferred to prepare a solvent. As long as the thermosetting resin composition can be formed into a layer form, the solvent can be used without any limitation. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyl. Ethyl acetate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate (eg methyl oxyacetate, Ethyl oxyacetate, butyl oxyacetate (such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)) And alkyl 3-oxopropionates (for example, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropane) Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-oxopropionate (for example: methyl 2-oxypropionate, 2 Ethyl oxypropionate, propyl 2-oxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2 -methyl ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate Ethyl 2-oxo-2-methylpropanoate (e.g., methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, etc.), pyruvate Ester, ethyl pyruvate, propyl pyruvate, methyl acetate methyl acetate, ethyl acetate ethyl acetate, methyl 2-oxobutyrate, ethyl 2-oxobutanoate, etc., and, as ethers, for example Suitable are diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol single Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, and the like, and aromatic hydrocarbons. For example, toluene, xylene, anisole, limonene, and the like are preferably exemplified, and as the fluorene, dimethyl hydrazine is preferably exemplified.

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. In this case, it is particularly preferably a mixed solution comprising methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, and lactate B selected from the above Ester, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl azine, B Two or more kinds of carbamide alcohol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

When the thermosetting resin composition contains a solvent, the content of the solvent is preferably such that the total solid content concentration of the thermosetting resin composition is 5% by mass to 80% by mass. More preferably, the total solid content concentration of the thermosetting resin composition is 5% by mass to 70% by mass, and particularly preferably the total solid content of the thermosetting resin composition is 10% by mass to 60% by mass. The amount of %. 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.

<<Interfacial Active Agent>> In the thermosetting resin 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, since the liquid property (particularly fluidity) at the time of preparation as a coating liquid is further improved by containing a fluorine-based surfactant, 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. Fluorine content rate The fluorine-based surfactant in this range is effective from the viewpoint 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).

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) Made) and so on.

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 thermosetting resin 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 thermosetting resin composition. quality%. 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.

<<Other Additives>> The thermosetting resin composition of the present invention may be formulated with various additives such as a hardener, a hardening catalyst, a decane coupling agent, a filler, and an adhesive, as long as the effects of the present invention are not impaired. Promoters, antioxidants, UV absorbers, anti-agglomerants, etc., anti-corrosion agents. When the additives are blended, the total amount of the additives is preferably 3% by mass or less of the solid content of the thermosetting resin composition.

<Preparation of Thermosetting Resin Composition> The thermosetting resin composition of 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.

<Application of Thermosetting Resin Composition> The thermosetting resin composition of the present invention can form a cured film having excellent heat resistance and insulating properties, and therefore can be preferably used for an insulating film of a semiconductor element or an interlayer insulating film for rewiring. Wait. In particular, it can be preferably used for an interlayer insulating film for rewiring or the like in a three-dimensional mounting element. Further, it can also be used for a photoresist (galvanic resist, etching resist, solder top resist) for electronics. In addition, it can also be used in the manufacture of layouts such as lithographic or screen layouts, in the use of etching of formed parts, electronics, in particular in the manufacture of protective coatings and dielectric layers in microelectronics.

<Method of Forming Cured Film> Next, a method of forming the cured film of the present invention will be described. The method for forming a cured film of the present invention includes a step of applying the thermosetting resin composition of the present invention to a substrate, and a step of curing the thermosetting resin composition for use on the substrate.

<<Step of Applying Thermosetting Resin Composition to Substrate>> As a method of applying the thermosetting resin composition to the substrate, spin coating, dipping, blade coating, suspended casting (suspended casting) The reason why the coating, the spraying, the electrostatic spraying, the reverse roll coating, and the like can be uniformly applied to the substrate is preferably electrostatic spraying or reverse roll coating. For example, the photosensitive layer may be introduced onto a temporary flexible carrier as in the case of a copper film printed circuit board by movement of a layer caused by the buildup, and then applied to the final substrate.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material. Examples of the inorganic substrate include glass, quartz, tantalum, tantalum nitride, and a composite substrate obtained by vapor-depositing molybdenum, titanium, aluminum, copper, or the like on the substrate. The examples include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polyfluorene, polyether. Bismuth, polyarylate, allyl diglycol carbonate, polyamidamine, 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, cross-linked fumaric acid diester, A synthetic resin such as a cyclic polyolefin, an aromatic ether, a maleimide-olefin, a cellulose, or an episulfide compound is used as a substrate of a resin. These substrates are used in a small form as described above. Generally, depending on the form of the final product, for example, a multilayer laminated structure such as a thin film transistor (TFT) device is formed.

The amount of the thermosetting resin composition (thickness of the layer) and the type of the substrate (the carrier of the layer) depend on the field of the intended use. It is particularly advantageous that the thermosetting resin composition can be used in a thickness of a layer which can be widely changed. The thickness of the layer is preferably in the range of 0.5 μm to 100 μm.

It is preferred to apply the thermosetting resin 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. <<Heating Step>> The thermosetting resin composition applied to the substrate is heated, whereby the thermosetting resin is subjected to a cyclization reaction to form a cured film having excellent heat resistance. The heating temperature is preferably from 50 ° C to 300 ° C, more preferably from 100 ° C to 200 ° C, particularly preferably from 100 ° C to 180 ° C. According to the present invention, the amine species produced by the compound represented by the formula (1) functions as a catalyst for the cyclization reaction of the thermosetting resin, and the cyclization reaction of the thermosetting resin can be promoted. The cyclization reaction of the thermosetting resin is carried out at a low temperature. Therefore, even at a low temperature treatment of 200 ° C or lower, a cured film excellent in heat resistance can be formed.

In the present invention, a pattern forming step may be performed between the step of applying the thermosetting resin composition on the substrate and the heating 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. A case where pattern formation is performed by photolithography will be described.

<<Exposure Step>> In the exposure step, the actinic ray or radiation corresponding to a predetermined pattern is applied to the thermosetting resin composition used for the substrate. The wavelength of the actinic ray or radiation varies depending on the composition of the thermosetting 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 500 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. Furthermore, photopolymerization of (meth) acrylates and similar olefinically unsaturated compounds is known, in particular, from thin oxygen in the air 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 thermosetting 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 thermosetting resin composition can be used.

In the field of the method for forming a cured film to which the present invention can be applied, it can be preferably used for an insulating film of a semiconductor element, an interlayer insulating film for rewiring, or the like. In particular, since it has good resolution, it can be preferably used for an interlayer insulating film for rewiring in a three-dimensional mounting element. Further, it can also be used for a photoresist (galvanic resist, etching resist, solder top resist) for electronics. In addition, it can also be used in the manufacture of layouts such as lithographic or screen layouts, in the use of etching of formed parts, electronics, in particular in the manufacture of protective coatings and dielectric layers in microelectronics.

<Semiconductor Element> Next, an embodiment of a semiconductor element in which the thermosetting resin composition of the present invention is used for an interlayer insulating film for rewiring 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 using the thermosetting 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. [Examples]

Hereinafter, the present invention will be more specifically described by the examples, but the present invention is not limited to the following examples as long as the present invention does not exceed the gist of the invention. In addition, "%" and "parts" are quality standards unless otherwise specified.

(Synthesis Example of Compound represented by General Formula (1)) [A-1 to A-10] 5 ml of water was added to a 50 ml eggplant type flask, and stirred at 5 ° C or lower for 5 minutes. Add 23 mmol of sodium hydroxide and add 23 mmol of chloroacetic acid. The corresponding arylamine, or allylamine was added dropwise to 10 mM, and 4.6 millimoles of potassium iodide was added. The temperature was raised to 90 ° C and stirred for 5 hours. After standing to cool to room temperature, the precipitated solid was filtered. The obtained solid was reslurryed in 2 ml of water, and then air-dried to obtain a target.

(Synthesis Example of Comparative Compound) [X-7, X-8] 5 ml of water and aniline 10 mmol and glutaconic acid or maleic acid 10 mmol were added to a 50 ml eggplant type flask. Stir for 5 minutes. Sodium hydroxide was added at 23 mM and heating was continued at 100 ° C for 24 hours. After standing to cool to room temperature, the precipitated solid was filtered. The obtained solid was reslurryed in 2 ml of water, and then air-dried to obtain a target.

(Synthesis Example 1) [Polyimine precursor resin derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine and 3-hydroxybenzyl alcohol (B-1; having no ethylenic unsaturated bond) Synthesis of Polyimine Precursor Resin] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxyl group The benzyl alcohol was suspended in 50 ml of N-methylpyrrolidone and dried using molecular sieves. The suspension was heated at 100 ° C for 3 hours. A clear solution was obtained after a few minutes of heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. Then, the reaction mixture was cooled to -10 ° C while maintaining the temperature at -10 ° C ± 4 ° C, and 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increases. After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine dissolved in 100 ml of N-methylpyrrolidone at 20 ° C to 23 ° C for 20 minutes. It was added dropwise to the reaction mixture. The reaction mixture was then stirred at room temperature for 1 night. Then, the polyimine precursor resin was precipitated in 5 liters of water, and the water-polyimine precursor resin mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor resin was filtered, removed, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimine precursor resin was dried at 45 ° C for 3 days under reduced pressure.

(Synthesis Example 2) [Polyimine precursor resin derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine and benzyl alcohol (B-2; polyazide having no ethylenic unsaturated bond) Synthesis of amine precursor resin] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 ml The N-methylpyrrolidone is dried using molecular sieves. The suspension was heated at 100 ° C for 3 hours. A clear solution was obtained after a few minutes of heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. Then, the reaction mixture was cooled to -10 ° C while maintaining the temperature at -10 ° C ± 4 ° C, and 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. During the addition of SOCl ₂ , the viscosity increases. After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine dissolved in 100 ml of N-methylpyrrolidone at 20 ° C to 23 ° C for 20 minutes. It was added dropwise to the reaction mixture. The reaction mixture was then stirred at room temperature for 1 night. Then, the polyimine precursor resin was precipitated in 5 liters of water, and the water-polyimine precursor resin mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor resin was filtered, removed, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimine precursor resin was dried at 45 ° C for 3 days under reduced pressure.

(Synthesis Example 3) [Polyimine precursor resin derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine and 2-hydroxyethyl methacrylate (B-3; having ethylenic unsaturation) Synthesis of Key Polyimine Precursor Resin] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of methyl 2-hydroxyethyl acrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at 60 ° C for 18 hours to produce pyromellitic acid and Diester of 2-hydroxyethyl methacrylate. Then, after the obtained diester was chlorinated by SOCl ₂ , it was converted into a polyimide precursor resin by 4,4'-oxydiphenylamine in the same manner as in Synthesis Example 1, and The polyimine precursor resin was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 4) [Polyimine precursor resin derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, 3-hydroxybenzyl alcohol, and 2-hydroxyethyl methacrylate (B-4) Synthesis of polyimine precursor resin having ethylenic unsaturated bond] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 m) Mixing 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme, and stirring at 60 ° C for 18 hours. A diester of pyromellitic acid and 2-hydroxyethyl methacrylate is produced. Separately, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol were suspended in 50 ml of N- The methylpyrrolidone was dried by a molecular sieve, and then the suspension was heated at 100 ° C for 3 hours to produce a diester of pyromellitic acid and 3-hydroxybenzyl alcohol. The sulfonate of the diester of pyromellitic acid and 2-hydroxyethyl methacrylate and the equimolar mixture of the pyromellitic acid and the diester of 3-hydroxybenzyl alcohol by SOCl ₂ are combined with the synthesis example. The same method was carried out by converting 4,4'-oxydiphenylamine into a polyimide precursor resin, and a polyimine precursor resin was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 5) [Polyimine precursor resin derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, benzyl alcohol and 2-hydroxyethyl methacrylate (B-5; having ethylene Synthesis of polyunsine precursor resin of unsaturated bonds] 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglyme, and stirred at 60 ° C for 18 hours to produce benzene A diester of tetracarboxylic acid and 2-hydroxyethyl methacrylate. Separately, 14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours) and 14.22 g (131.58 mmol) of benzyl alcohol were suspended in 50 ml of N-methylpyrrole. The ketone was dried by a molecular sieve, and then the suspension was heated at 100 ° C for 3 hours to produce a diester of pyromellitic acid and benzyl alcohol. The same ester as in Synthesis Example 1 was obtained by chlorinating a diester of pyromellitic acid with 2-hydroxyethyl methacrylate and a molar mixture of pyromellitic acid and a diester of benzyl alcohol by SOCl ₂ . The method was converted into a polyimine precursor resin by 4,4'-oxydiphenylamine, and a polyimine precursor resin was obtained in the same manner as in Synthesis Example 1.

<Base generation temperature> Using a differential scanning calorimeter (manufactured by Q2000 TA Co., Ltd.), the specific compound (A) was heated to 250 ° C at 5 ° C / min in a pressure resistant capsule, and the peak temperature of the heat generation peak having the lowest temperature was read. The peak temperature was measured as the alkali generation temperature.

<Test Example 1> [Examples 1 to 20, Comparative Examples 1 to 9] The components described below were mixed to prepare a coating liquid of a thermosetting resin composition. <Composition of thermosetting resin composition> (A) Specific compound: Mass % shown in Table 1 (B) Polyimine precursor resin: Mass % shown in Table 1 (C) Polymerizable compound: Table 1 % by mass (D) Thermal polymerization initiator: % by mass as stated in Table 1 (other components) γ-butyrolactone: 60% by mass

Each thermosetting resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then spin-coated on a tantalum wafer (3500 rpm, 30 seconds) for application. The tantalum wafer to which the thermosetting resin composition was applied was dried at 100 ° C for 5 minutes on a hot plate to form a uniform resin layer having a thickness of 10 μm on the tantalum wafer.

[Example 21] <Composition of Thermosetting Resin Composition> (A) Specific Compound: Mass % shown in Table 1 (B) Polyimine precursor resin: Mass % shown in Table 1 (C) Polymerizable compound : mass % (E) photopolymerization initiator described in Table 1: mass% (other components) described in Table 1 γ-butyrolactone: 60% by mass

The thermosetting resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then spin-coated on a tantalum wafer (3,500 rpm, 30 seconds) for application. The tantalum wafer to which the thermosetting resin composition was applied was dried at 100 ° C for 5 minutes on a hot plate, and a uniform film having a thickness of 10 μm was formed on the tantalum wafer using an aligner (Karl-Suss MA150). Exposure was performed at 500 mJ. Exposure was performed using a high pressure mercury lamp to measure the exposure energy at a wavelength of 365 nm.

<Evaluation> [Curability] The thermosetting resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then applied by spin coating on a crucible wafer (1200 rpm, 30 seconds). The tantalum wafer to which the thermosetting resin composition was applied was dried at 100 ° C for 5 minutes on a hot plate to form a uniform film having a thickness of 10 μm on the tantalum wafer. The film was peeled off from the wafer, and subjected to thermogravimetric analysis (Thermal Gravimetric Analysis (TGA) measurement) in a state of maintaining at 250 ° C in nitrogen, and the cyclization time was evaluated. The polyimine precursor resin was accompanied by the progress of the cyclization reaction, and the mass was reduced. Therefore, the time until no mass reduction occurred was evaluated by the following criteria. The shorter the time, the faster the cyclization speed becomes, and it becomes a better result. A: more than 10 minutes and 30 minutes or less B: more than 30 minutes and 60 minutes or less C: more than 60 minutes and 120 minutes or less D: more than 200 minutes. Or not cyclized.

[Stability] After preparing a thermosetting resin composition, a container containing 10 g of a thermosetting resin composition was sealed, and allowed to stand in an environment of 25 ° C and a humidity of 65%. The stability was evaluated by cyclization with a thermosetting resin composition until the solid was precipitated. The longer the time, the higher the stability of the composition, which is a better result. The precipitation of the solid was carried out by using a mesh having a pore diameter of 0.8 μm, and visually observing the presence or absence of a foreign matter in the form of a mesh. A: No precipitation of solids was observed for more than 30 days. Solids were precipitated over 20 days and 30 days. Solids were precipitated over 10 days and 20 days. Solids were precipitated over 5 days and 10 days. E: solid precipitation within 5 days

[Heat Resistance] The film was peeled off from the silicon wafer, and subjected to thermogravimetric analysis (TGA measurement) in a state of maintaining at 350 ° C for 3 hours in nitrogen gas, and the mass reduction rate was evaluated. The heat resistance was evaluated by the following criteria. The smaller the mass reduction rate after 3 hours, the higher the heat resistance, which is a preferable result. As a result of the evaluation, it is preferably A to C in practical use. A: 1% by mass or less B: more than 1% by mass and 5% by mass or less C: More than 5% by mass and 10% by mass or less D: More than 10% by mass

From the results, it was found that the thermosetting resin compositions of Examples 1 to 21 were excellent in curability and stability. On the other hand, at least one of the curable properties and the stability of the thermosetting resin composition of Comparative Examples 1 to 9 was inferior to the thermosetting resin composition of the example.

The abbreviations described in Table 1 are as follows. (A) Specific Compounds·A-1 to A-12: The following structures (wherein Me represents a methyl group). [Table 2] X-1 to X-8 (comparative compound): The following structure (wherein Me represents a methyl group).

(B) Polyimine precursor resin B-1 to B-5: Polyimine precursor resin B-1 to polyimine precursor resin B-5 synthesized in Synthesis Example 1 to Synthesis Example 5

(C) Polymeric compound C-1: NK ester (NK ESTER) M-40G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., monofunctional methacrylate, the following structure) [Chem. 20] C-2: NK Ester 4G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., difunctional methacrylate, the following structure) [Chem. 21] (C-3) NK ester (NK ESTER) A-9300 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., trifunctional acrylate, the following structure) [Chem. 22]

(D) Thermal polymerization initiator D-1: Perbutyl Z (manufactured by Nippon Oil Co., Ltd., tert-butyl peroxybenzoate, decomposition temperature (10-hour half-life temperature = 104 ° C))

(E) Photopolymerization initiator E-1: IRGACURE OXE-01 (manufactured by BASF Corporation) [Chem. 23]

<Example 100> The thermosetting resin composition of Example 1 was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then spin-coated on a resin substrate on which a copper thin layer was formed (3500 rpm, 30 seconds) to apply. The thermosetting resin composition applied to the resin substrate was dried at 100 ° C for 5 minutes. Then, heating was carried out at 180 ° C for 20 minutes. In this manner, an interlayer insulating film for rewiring is formed. The interlayer insulating film for rewiring is excellent in insulation properties. In addition, as a result of manufacturing the semiconductor element using the interlayer insulating film for rewiring, it was confirmed that the operation was performed without any problem. Further, the same effect can be obtained even if the polyimine precursor resin is changed to a polyamidoximine precursor resin or a polybenzoxazole precursor.

100‧‧‧Semiconductor components
101a～101d‧‧‧ semiconductor devices
101‧‧‧Layer
102b～10d‧‧‧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 of the present invention.

100‧‧‧Semiconductor components

101a~101d‧‧‧ semiconductor devices

101‧‧‧Layer

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 (14)

A thermosetting resin composition comprising a compound represented by the following formula (1) and a thermosetting resin which is cyclized with a base and hardened; In the formula (1), A 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 thermosetting resin composition according to claim 1, wherein in the above formula (1), A is an aromatic ring group. The thermosetting resin composition according to Item 1 or 2, wherein in the above formula (1), A is a benzene ring. The thermosetting resin composition according to claim 1 or 2, wherein in the formula (1), L ¹ and L ² are each independently an alkylene group. The thermosetting resin composition according to the first or second aspect of the invention, wherein m, n and p are each in the formula (1). The thermosetting resin composition according to Item 1 or 2, wherein the compound represented by the above formula (1) is N-aryliminodiacetic acid. The thermosetting resin composition according to claim 1 or 2, wherein the thermosetting resin is selected from the group consisting of a polyimide precursor resin, a polyamidamine precursor resin, and a poly At least one of the benzoxazole precursor resins. The thermosetting resin composition according to claim 1 or 2, wherein the thermosetting resin has an ethylenically unsaturated bond. The thermosetting resin composition according to claim 1 or 2, further comprising a compound having an ethylenically unsaturated bond as a polymerizable compound. The thermosetting resin composition according to claim 8, which further comprises a photopolymerization initiator. A cured film obtained by curing the thermosetting resin composition according to any one of the first to tenth aspects of the invention. The cured film according to claim 11, which is an interlayer insulating film for rewiring. A method for producing a cured film, comprising: a step of applying a thermosetting resin composition according to any one of claims 1 to 10 to a substrate, and a corresponding substrate for use on the substrate The step of hardening the thermosetting resin composition. A semiconductor element comprising the cured film as described in claim 11 or a cured film produced by the method of claim 13 of the patent application.