TWI644979B - Thermosetting resin composition, cured film, method for producing cured film, and semiconductor element - Google Patents

Abstract

The present invention provides a thermosetting resin composition capable of performing a cyclization reaction of a thermosetting resin at a low temperature and having excellent stability, a cured film using the thermosetting resin composition, a method for producing a cured film, and a semiconductor device. The thermosetting resin composition includes a compound represented by the general formula (1) and a thermosetting resin that is cyclized and hardened. In the general 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, m represents an integer of 1 or more, and n Represents an integer of 1 or more, and p represents an integer of 1 or more.

Description

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

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

Thermosetting resins that cyclize and cure polyimide resins, polyimide resins, and polybenzoxazole resins, etc., are excellent in heat resistance and insulation properties, and are therefore used as insulating layers for semiconductor devices .

In addition, since the thermosetting resin has low solubility in a solvent, precursor resins before the cyclization reaction (polyimide precursor resin, polyimide precursor resin, polybenzoxazole The precursor resin is used in a state of being applied to a substrate or the like, followed by heating and cyclizing the thermosetting resin to form a cured film.

For example, Patent Documents 1 and 2 disclose a composition including a polyfluorene imide precursor resin having a radical polymerizable group and a photopolymerization initiator.

Patent Document 3 discloses a composition containing an ester of a polyamine having a photopolymerizable olefin double bond in an ester group.

Patent Document 4 discloses a composition including a polyimide precursor resin and a compound that 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 polyfluorene imide precursor resin composition including a polyfluorene imide precursor and a thermal alkali generator containing thermal decomposition caused by heating at a temperature of 200 ° C or lower. Neutral compounds of secondary amines; and solvents.

On the other hand, Patent Document 7 discloses a lithographic printing plate precursor having an image forming layer containing an infrared absorber, a polymerization initiator, a polymerizable compound, a hydrophobic adhesive, and N- Phenyliminodiacetic acid.

In addition, Patent Document 8 discloses a laser-decomposable resin composition containing N-phenyliminodiacetic acid and a binder polymer.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 63-27834

[Patent Document 2] Japanese Patent Laid-Open No. 07-5688

[Patent Document 3] US Patent No. 4,548,891

[Patent Document 4] Japanese Patent Laid-Open No. 2003-084435

[Patent Document 5] Japanese Patent Laid-Open No. 2006-282880

[Patent Document 6] Japanese Patent Laid-Open No. 2007-56196

[Patent Document 7] Japanese Patent Laid-Open No. 2009-237175

[Patent Document 8] Japanese Patent Laid-Open No. 2008-63553

Thermosetting resins such as polyimide precursor resin, polyimide precursor resin, polybenzoxazole precursor resin, and the like, which are cyclized and cured with an alkali, can form a cured film with excellent heat resistance. However, a heat treatment at a high temperature is required for the cyclization reaction of these thermosetting resins. Therefore, when using such a thermosetting resin to form an insulating layer of a semiconductor element, etc., there is a possibility that thermal damage to electronic parts and the like may occur due to heating during the cyclization reaction of the thermosetting resin, and a cyclization temperature is required Further reduction.

The present inventors have studied the compositions disclosed in Patent Documents 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 insufficient.

Further, in Patent Document 5, as described in paragraph No. 0014, it is an invention for the purpose of providing a photosensitive resin composition that is large regardless of the type of the polyimide precursor resin. As a result of the solubility contrast, a sufficient process range can be maintained, and a pattern with a good shape can be obtained. In order to achieve this purpose, an N-aromatic glycine derivative is used as a photobase generator. That is, in Patent Document 5, the amine imidization of the polyfluorene imide precursor resin is performed using the amine generated by irradiating the N-aromatic glycine derivative with light as a catalyst, thereby curing the exposed portion, In addition, a poor solubility is provided between the exposed portion and the unexposed portion.

However, in Patent Document 5, no study on reducing the cyclization temperature has been performed. In the examples, heating was performed at 300 ° C. for 1 hour to carry out the imidization.

In addition, in Patent Document 6, a thermal base generator containing a neutral compound that causes thermal decomposition by heating at a temperature of 200 ° C. or lower to generate a secondary amine is used. However, it is known from the study of the inventors that the thermal base The generating agent is in a balanced state between dissociated and non-dissociated in the composition. Therefore, it can be seen that during the storage of the composition, the polyimide precursor resin undergoes a cyclization reaction and is liable to cause gelation and the like, and has poor stability.

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

Therefore, an object of the present invention is to provide a thermosetting resin composition which can perform a cyclization reaction of a thermosetting resin at a low temperature and has excellent stability, a cured film using the thermosetting resin composition, and the production of a cured film. Method and semiconductor element.

As a result of detailed investigations by the present inventors, it was found that cyclization of a thermosetting resin can be provided by using a compound represented by the following general formula (1) in combination with a thermosetting resin that is cyclized with a base and cured. The present invention has completed 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 general formula (1) and a thermosetting resin that is cyclized with a base and hardened; [化 1]

In the general 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, m represents an integer of 1 or more, and n Represents an integer of 1 or more, and p represents an integer of 1 or more.

<2> The thermosetting resin composition according to <1>, wherein in the general formula (1), A is an aromatic ring group.

<3> The thermosetting resin composition according to <1> or <2>, wherein in the general formula (1), A is a benzene ring.

<4> The thermosetting resin composition according to any one of <1> to <3>, wherein in the general formula (1), L ¹ and L ² are each independently an alkylene group.

<5> The thermosetting resin composition according to any one of <1> to <4>, wherein in the general formula (1), m, n, and p are each 1.

<6> The thermosetting resin composition according to any one of <1> to <5>, wherein the compound represented by the general formula (1) is N-arylimine diacetic acid.

<7> 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 polyimide precursor resin And at least one of polybenzoxazole precursor resins.

<8> The thermosetting resin composition according to any one of <1> to <7> Materials, in which the thermosetting resin has an ethylenically unsaturated bond.

<9> The thermosetting resin composition according to any one of <1> to <8>, which further includes a compound having an ethylenically unsaturated bond as a polymerizable compound.

<10> The thermosetting resin composition according to <8> or <9>, further comprising 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 redistribution.

<13> A method for producing a cured film, comprising: a step of applying the thermosetting resin composition according to any one of <1> to <10> on a substrate; and correspondingly applying heat to the substrate. A step of curing the curable resin composition.

<14> A semiconductor device comprising the cured film according to <11> or a cured film produced by the method according to <13>.

<15> A hot alkali generator, which is a compound represented by the following general formula (1);

In the general 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, m represents an integer of 1 or more, and n Represents an integer of 1 or more, and p represents an integer of 1 or more.

<16> The hot alkali generator according to <15>, wherein in the general formula (1), A is an aromatic ring group.

<17> The hot alkali generator according to <15> or <16>, wherein in the general formula (1), A is a benzene ring.

<18> The hot alkali generator according to any one of <15> to <17>, wherein in the general formula (1), L ¹ and L ² are each independently an alkylene group.

<19> The hot alkali generator according to any one of <15> to <18>, wherein in the general formula (1), m, n, and p are each 1.

<20> The hot alkali generator according to any one of <15> to <19>, wherein the compound represented by the general formula (1) is N-aryliminodiacetic acid.

According to the present invention, it is possible to provide a thermosetting resin composition capable of performing a cyclization reaction of a thermosetting resin at a low temperature and having excellent stability, a cured film using the thermosetting resin composition, a method for producing a cured film, and a method for producing the same. Semiconductor element.

100‧‧‧Semiconductor element

101a ~ 101d‧‧‧semiconductor device

101‧‧‧Laminated body

102b ~ 102d‧‧‧through electrode

103a ~ 103e‧‧‧Metal bump

105‧‧‧ redistribution layer

110, 110a, 110b‧‧‧ Underfill

115‧‧‧ Insulation

120‧‧‧ wiring board

120a‧‧‧ surface electrode

FIG. 1 is a schematic diagram showing a configuration of an embodiment of a semiconductor element according to the present invention.

The description of the constituent elements in the present invention described below may be based on this The representative embodiments of the invention are performed, but the present invention is not limited to such embodiments.

In the description of the group (atomic group) in the present specification, the descriptions of the substituted and unsubstituted expressions include a group (atomic group) having no substituent, and also include a group (atomic group) having a substituent. For example, the "alkyl group" includes not only an alkyl group (unsubstituted alkyl group) having no substituent, but also an alkyl group (substituted alkyl group) having a substituent.

In this specification, "actinic rays" means, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser light, extreme ultraviolet rays (Extreme Ultraviolet (EUV) light), X-rays, electron beams, etc. . In the present invention, light means actinic rays or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure with a mercury lamp, far-ultraviolet rays, X-rays, and EUV light typified by excimer laser light, but also particle beams such as electron beams and ion beams The depiction of is also included in the exposure.

In the present specification, a numerical range expressed using "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value.

In this specification, "(meth) acrylate" means both or both of "acrylate" and "methacrylate", and "(meth) allyl" means "allyl" and "Methallyl" or both, "(meth) acrylic" means both "acrylic" and "methacrylic", or either, "(meth) acryl" "" Means both "acrylfluorenyl" and "methacrylfluorenyl", or either.

In this manual, the term "step" means not only independent steps, In the case where it cannot be clearly distinguished from other steps, as long as the intended function of the step is achieved, it is also included in this term.

In the present specification, the solid content concentration refers to the mass percentage of the mass of other components other than the solvent with respect to the total mass of the composition. In addition, unless otherwise stated, solid content concentration means the density | concentration at 25 degreeC.

In this specification, the weight average molecular weight is defined as a polystyrene conversion value measured by gel permeation chromatography (GPC). In this specification, the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) can be obtained, for example, by using HLC-8220 (manufactured by Tosoh) and adding TSKgel Super AWM-H (Tosoh (stock) ), 6.0 mm inner diameter (Inner Diameter (ID) x 15.0 cm) was used as a pipe string to obtain it. Unless otherwise specified, the eluate was measured by 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 general formula (1) and a thermosetting resin which is cyclized with an alkali and hardened to be promoted.

With the thermosetting resin composition of the present invention, a cyclization reaction of the thermosetting resin can be performed at a low temperature, and a thermosetting resin composition having excellent stability can be obtained. This effect is presumed for the following reasons. That is, the compound represented by the general formula (1) is acidic at room temperature, but disappears by heating, decarboxylation or dehydration cyclization of the carboxyl group, whereby the neutralized and passivated amine site previously obtained becomes active, whereby Becomes alkaline. In addition, it is considered that the base generated by the compound represented by the free formula (1) is thermally hardened. The cyclization reaction of the resin is promoted. In addition, as described above, since the compound represented by the general formula (1) is acidic at room temperature, the cyclization reaction of the thermosetting resin cannot be promoted. Therefore, even if the compound represented by the general formula (1) is stored for a long period of time in a state of being mixed with a thermosetting resin which is cyclized with an alkali to promote hardening, the reaction does not proceed unless it is heated, so it is preferable. .

The present invention is described in detail below.

<< Compound represented by General formula (1) >>

The thermosetting resin composition of the present invention includes a compound represented by the general formula (1). This compound generates a base by heating and functions as a hot base generator. It usually exists as an acidic compound before heating. In addition, in the present specification, an acidic compound refers to a compound in which 1 g of the compound is extracted into a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio of water / tetrahydrofuran = 1/4) is added, and Stir at room temperature for 1 hour. The value of this solution measured at 20 ° C using a pH meter was less than 7.

In the general 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, m represents an integer of 1 or more, and n Represents an integer of 1 or more, p represents an integer of 1 or more

In the general formula (1), A represents a p-valent organic group. Examples of the organic group include an aliphatic group and an aromatic cyclic group, and an aromatic cyclic group is preferred. By using A as an aromatic ring group, a base with a high boiling point can be easily produced at a lower temperature. By increasing the boiling point of the generated alkali, it is difficult to volatilize or decompose by heating during curing of the thermosetting resin, and the 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 carbon number of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The alkyl group may be any of linear and branched. 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 third butyl group, and a dodecyl group.

The number of carbon atoms of the cycloalkyl group is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 10. The cycloalkyl group may have a substituent or may be unsubstituted. Specific examples of cycloalkyl include cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl.

The carbon number of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and even more preferably 2 to 10. The alkenyl group may be any of linear and branched. The alkenyl group may have a substituent or may be unsubstituted. Examples of the alkenyl group include a vinyl group and a (meth) allyl group.

Examples of the divalent or higher aliphatic group include a group obtained by removing one or more hydrogen atoms from the monovalent aliphatic group.

The aromatic ring group may be monocyclic or polycyclic. The aromatic ring group may 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 pentenene ring, an indene ring, a fluorene ring, a heptene ring, a dicyclopentadienyl ring, a fluorene ring, and a fused ring. Pentabenzene ring, pinene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, Chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring , Indoxazine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring , Quinoxazoline ring, isoquinoline ring, carbazole ring, morphine ring, acridine ring, morpholine ring, thiathracene ring, chromene ring, dibenzopiperan ring, phenoxaline The ring, the phenothiazine ring, and the phenazine ring are most preferably a benzene ring.

The aromatic ring group may have a plurality of aromatic rings connected through a single bond or a linking group described later. As the linking group, for example, an alkylene group is preferred. It is also preferable that the alkylene group is any of linear and branched. Specific examples of the aromatic ring group in which a plurality of aromatic rings are connected through a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, Tetraphenylmethane, etc.

Examples of the substituent which the organic group represented by A may have include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group, and a third butoxy group Aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; ethoxyl, propoxyl, and benzyloxy Isofluorenyl groups; ethylfluorenyl groups such as ethylfluorenyl, benzamidine, isobutylfluorenyl, acrylfluorenyl, methacrylfluorenyl, and methoxysulfenyl groups; alkylmercapto groups such as methylmercapto and tertiary butylmercapto; Aryl mercapto groups such as phenyl mercapto and p-tolyl mercapto; alkyl groups such as methyl, ethyl, third butyl, and dodecyl; cyclopentyl, cyclohexyl, cycloheptyl, Cycloalkyl groups such as adamantyl; aryl groups such as phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl, and phenanthryl; hydroxyl; carboxyl; formamyl; sulfo; cyano; alkane Arylaminocarbonyl; arylaminocarbonyl; sulfonamido; silyl; amine; monoalkylamino; dialkylamino; arylamino; and diarylamino; thiooxy; Or a combination of these.

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- , alkylene (preferably carbon number) 1 to 10 straight-chain alkylene or branched alkylene), cycloalkylene (preferably a cycloalkylene having 3 to 10 carbon atoms), and alkenyl (preferably a straight-chain alkylene having 1 to 10 carbon atoms) An alkenyl group or a branched alkenyl group) or a linking group in which a plurality of these are connected. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group, an alkylene group, more preferably a linear alkylene group or a branched alkylene group, and even more preferably a linear alkylene group, and particularly preferably an alkylene group or ethylene The methyl group is particularly preferably a methylene group.

m and n each represent an integer of 1 or more, preferably 1 or 2, and 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, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower. Furthermore, the stability of a thermosetting resin composition can be improved.

p represents an integer of 1 or more, preferably 1 or 2, and more preferably 1. The upper limit of p is the maximum number of substituents that can be used for the organic group represented by A. When p is 1, a tertiary amine having a high boiling point is easily generated by heating at 200 ° C or lower.

The compound represented by the general formula (1) is preferably N-aryliminodiacetic acid. N-aryliminodiacetic acid is a compound in which A in the general formula (1) is an aromatic ring group, L ¹ and L ² are a methylene group, m is 1, n is 1, and p is 1. N-aryliminodiacetic acid easily generates tertiary amines with high boiling points by heating below 200 ° C.

The compound represented by the general formula (1) is preferably a compound that generates a base when heated to 120 ° C to 230 ° C, and more preferably a compound that generates a base at 120 ° C to 200 ° C. The alkali generation temperature can be measured using differential scanning calorimetry. The compound is heated to 250 ° C at 5 ° C / min in a pressure-resistant capsule, the peak temperature of the lowest exothermic peak is read, and the peak temperature is used as the alkali generation temperature. Perform the measurement.

The base generated by the compound represented by the general formula (1) is preferably a secondary amine or a tertiary amine, and more preferably a tertiary amine. Since tertiary amines are highly basic, the cyclization temperature of the thermosetting resin can be further reduced.

The boiling point of the base generated by the compound represented by the general formula (1) is preferably 80 ° C or higher, more preferably 100 ° C or higher, and even more preferably 140 ° C or higher. The molecular weight of the generated base is preferably 80 to 2,000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. In addition, the molecular weight value is a theoretical value calculated | required from a structural formula.

Specific examples of the compound represented by the general formula (1) are described below, but the present invention is not limited to these specific examples. These can be used individually or in mixture of 2 or more types. Note that Me in the following formula represents a methyl group. Among the compounds shown below, (A-1) to (A-9), (A-13) to (A-17), (A-19), (A-20) are more preferable, (A-1), (A-2), (A-3), (A-4), (A-8), (A-9), (A-19).

[Chemical 4]

The content of the compound represented by the general formula (1) with respect to the total solid content of the thermosetting resin composition of the present invention is preferably from 0.1% by mass to 50% by mass. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and even more preferably 20% by mass or less. When the content of the compound represented by the general formula (1) is within the above range, cyclization of the thermosetting resin can be performed at a low temperature, and a cured film having excellent heat resistance can be formed by heat treatment at a low temperature.

The thermosetting resin composition of the present invention preferably contains 0.1 to 30 parts by mass of the compound represented by the general formula (1) with respect to 100 parts by mass of the thermosetting resin, and more preferably contains 1 part by mass to 20 parts by mass.

As the compound represented by the general formula (1), one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the range.

<< Thermosetting resin >>

The thermosetting resin composition of the present invention includes a thermosetting resin that is cyclized with an alkali and promotes hardening. The thermosetting resin is preferably a heterocyclic-containing polymer precursor resin that generates a cyclization reaction by heating and can form a heterocyclic-containing polymer. As the heterocyclic-containing polymer precursor resin, one or more selected from the group consisting of a polyimide precursor resin, a polyimide precursor resin, and a polybenzoxazole precursor resin, more preferably It is a polyfluorene imide precursor resin or a polybenzoxazole precursor resin, and more preferably a polyfluorene imide precursor resin. According to this aspect, a cured film having more excellent heat resistance is easily formed. In addition, these thermosetting resins have a high cyclization temperature and were previously heated to 300 ° C or higher for cyclization. However, according to the present invention, even these thermosetting resins can be used at 300 ° C or lower (preferably 200 ° C. or less, more preferably 180 ° C. or less) to sufficiently advance the cyclization reaction, so that the effects of the present invention can be more significantly obtained.

In the present invention, the thermosetting resin is preferably a polyfluorene imide precursor resin having an ethylenically unsaturated bond, and more preferably an ethylenically unsaturated bond. Since the thermosetting resin has an ethylenically unsaturated bond, it is easy to form a cured film having more excellent heat resistance. Furthermore, when patterning is performed by photolithography, sensitivity can be improved.

The content of the thermosetting resin in the thermosetting resin composition of the present invention is preferably 30% 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 even more preferably 50% by mass or more.

<<< Polyimide precursor resin, Polyamidide imide precursor resin >>>

The polyfluorene imide precursor resin is not particularly limited as long as it is a compound capable of polyimidization, but a polyfluorene imide precursor resin having an ethylenically unsaturated bond is preferred.

In addition, the polyamidoamine imine precursor resin is not particularly limited as long as it is a compound capable of polyamidoaminium imidization, but a polyamidoamine imine precursor having an ethylenically unsaturated bond is preferred. Resin.

The polyamidoimide precursor resin and polyamidoimide precursor resin are preferably compounds containing a repeating unit represented by the following general formula (2).

In the general 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 each independently represent A hydrogen atom or a monovalent organic group.

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

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include diamine residues remaining after 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 following diamine residues etc. which remain after removal of the amine group of the diamine are mentioned.

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 di 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 Hydrazone and 3,3'-diaminodiphenylphosphonium, 4,4'-diaminodiphenylsulfide and 3,3'-diaminodiphenylsulfide, 4,4'-diaminediphenyl 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) Alkane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4- Aminophenyl) hexafluoropropane, 4,4'-diamino p-terphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy Phenyl) phenyl] fluorene, bis [4- (3-aminophenoxy) phenyl] fluorene, bis [4- (2-aminophenoxy) phenyl] fluorene, 1,4-bis (4 -Aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'-dimethyl-4,4'-diaminodiphenylphosphonium, 1,3- Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, bis [4- (4- Aminophenoxy)] phenyl ether, 3,3'-diethyl -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9- Bis (4-aminophenyl) -10-hydroanthracene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1, 4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) Samarium, 4,4'-dimethyl-3,3'-diaminodiphenylphosphonium, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane , 2,4-diaminocumene and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl -P-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisilaxane, 2,7-diaminofluorene, 2,5 -Diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzidineaniline, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diamine Trifluorotoluene, diaminoanthraquinone, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-Aminophenyl) decafluoro Alkane, 1,7-bis (4-aminophenyl) tetradefluorofluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane , 2,2-bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethyl) Phenylphenoxy) benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethyl) (Phenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylphosphonium, 4,4'-bis (3-amino-5-trifluoro Methylphenoxy) diphenylphosphonium, 2,2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5 '-Tetramethyl-4,4'-diaminobiphenyl, 2,2', 5,5 ', 6,6'-hexafluorobenzylamine and 4,4'-diaminobiphenyl Diamine residues that remain after the amine groups of at least one diamine are removed.

R ¹¹² represents a tetravalent organic group. Examples of the tetravalent organic group include a tetracarboxylic acid residue remaining after removing the anhydride group from the tetracarboxylic dianhydride.

Specific examples thereof include tetracarboxylic acid residues remaining after removing anhydride groups from the following tetracarboxylic dianhydrides.

Selected from the group consisting of pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfide tetracarboxylic acid Dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4, 4'-diphenylmethanetetracarboxylic dianhydride, 2,2 ', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride , 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, dianhydride of oxydiphthalic acid, 3,3,, 4,4'-diphenyl oxide tetracarboxylic acid Dianhydride, 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-fluorenetetracarboxylic 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-dicarboxyphenyl) Among ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and at least one of these C1-C6 alkyl derivatives and C1-C6 alkoxy derivatives, among tetracarboxylic dianhydrides Residual tetracarboxylic acid residue after removal of anhydride group.

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 that improves the solubility of the developing solution can be preferably used.

From the viewpoint of the solubility of the aqueous developer, R ¹¹³ and R ^{114 are} preferably a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include an aryl group and an aralkyl group having one, two, or three, preferably one, acidic groups bonded to an aryl carbon. Specific examples 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 specific examples include a phenyl group having an acidic group and a benzyl group having an acidic group. 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, they have good solubility in an aqueous developer, and are particularly suitable for use as a negative thermosetting resin.组合 物。 Composition.

From the viewpoint of the solubility of an organic solvent, R ¹¹³ and R ^{114 are} preferably a monovalent organic group. As the monovalent organic group, an alkyl group, a cycloalkyl group, and an aromatic ring group are particularly preferred.

The alkyl group is specifically preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, second butyl, third 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 cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic cycloalkyl group include adamantyl, norbornyl, norbornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, and fluorene. Group, dicyclohexyl and pinenyl. Among them, from the viewpoint of coexistence with high sensitivity, it is best to surround yourself. base.

As the aromatic ring group, specifically, a substituted or unsubstituted benzene ring, a naphthalene ring, a pendene ring, an indene ring, a fluorene ring, a heptene ring, a dicyclopentadiene benzene ring, and arsine Ring, fused pentaphenyl ring, pinene ring, phenanthrene ring, anthracene ring, fused tetraphenyl ring, Ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indazine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinazine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, iso A quinoline ring, a carbazole ring, a pyridine ring, an acridine ring, a phenanthroline ring, a thiathracene ring, a chromene ring, a dibenzopiperan ring, a phenoxaline ring, a phenothiazine ring, or a phenazine ring. The best is benzene ring.

In the general formula (2), at least one of R ¹¹³ and R ¹¹⁴ preferably represents a polymerizable group. Thereby, sensitivity and 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. Base etc. Among them, a group having an ethylenically unsaturated bond is preferred for reasons of good sensitivity. 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).

In the formula (III), R ²⁰⁰ represents hydrogen or a methyl group, and more preferably a methyl group.

In 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 ethylene, propyl, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, and hexamethylene. , Octamethylene, dodecylmethylene, -CH ₂ CH (OH) CH _2- , more preferably ethylene, propyl, trimethylene, -CH ₂ CH (OH) CH _2- .

Particularly preferably, R ²⁰⁰ is methyl, and R ²⁰¹ is ethylene.

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

The polyimide precursor resin and the polyimide precursor resin may contain, in addition to all of the repeating structural units of the general formula (2) based on one kind of R ¹¹¹ or R ¹¹² , a polyimide precursor resin. 2 or more different kinds of repeating units. In addition, the polyimide precursor resin and the polyimide precursor resin may contain repeating units which are structural isomers with each other. As a representation of a structural isomer pair of a unit of the general formula (2), for example, the following shows 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-).

In addition to the repeating unit of the general formula (2), the polyfluorene imine precursor resin and the polyfluorene imine precursor resin may contain other kinds of repeating structural units.

[Chemical 7]

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

<<< Polybenzoxazole precursor resin >>>

The polybenzoxazole precursor resin is not particularly limited as long as it is a compound capable of undergoing polybenzoxazole conversion, but a polybenzoxazole precursor resin having an ethylenically unsaturated bond is preferred. In particular, a compound represented by the following general formula (3) is preferable.

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

R ¹²¹ represents a divalent organic group. The divalent organic group is preferably an aromatic ring group. Examples of the aromatic ring group include the following.

In the formula, A represents a divalent group selected from the group consisting of -CH _2- , -O-, -S-, -SO _2- , -CO-, -NHCO-, and -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 general formula (A).

Ar (NH ₂ ) ₂ (OH) ₂ . ． ． (A)

In the formula, Ar is an aryl group.

Examples of the bisphenol of the general formula (A) include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, and 4,4'- Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylphosphonium, 4,4'-diamino-3,3'-di Hydroxydiphenylphosphonium, 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-hydroxy Phenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-di Amino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'- Dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino- 2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. These bisaminophenols can be used alone or in combination.

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

In the formula, X ₁ represents -O-, -S-, -C (CF ₃ ) _2- , -CH _2- , -SO _2- , -NHCO-. In addition, in the structure, -OH and -NH ₂ contained in the structure of the general formula (A) are mutually bonded to an adjacent position (adjacent position).

R ¹²³ and R ¹²⁴ represent a hydrogen atom or a monovalent organic group, and it is preferred that at least one of R ¹²³ and R ¹²⁴ represents a polymerizable group. The polymerizable group is the same as that described in R ¹¹³ and R ¹¹⁴ of the general formula (2), and the preferable ranges are also the same.

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

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

<< Polymerizable compound >>

The thermosetting resin composition of the present invention may contain the compound represented by the general 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. Furthermore, pattern formation can also be performed by photolithography.

The polymerizable compound is a compound having a polymerizable group, and a known compound that can be polymerized by a radical can be used. The polymerizable group refers to a group that can be polymerized by the action of actinic rays, radiation, or radicals, and examples thereof include groups having an ethylenically unsaturated bond. The group having an ethylenically unsaturated bond is preferably a styryl group, a vinyl group, a (meth) acrylfluorenyl group, and a (meth) allyl group, and more preferably a (meth) acrylfluorenyl 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 even more preferably Is an acrylate compound.

The polymerizable compound is widely known in the industrial field, and these polymerizable compounds can be used in the present invention without particular limitation. The polymerizable compounds may be, for example, any one of chemical forms such as monomers, prepolymers, oligomers, or mixtures thereof, and such multimers.

In the present invention, a monomeric polymerizable compound (hereinafter, also referred to as a polymerizable monomer) is a compound different from a polymer compound. The polymerizable monomer is typically a low-molecular compound, preferably a low-molecular compound having a molecular weight of 2,000 or less, more preferably a low-molecular compound having a molecular weight of 1500 or less, and even more preferably a low-molecular compound having a molecular weight of 900 or less. The molecular weight of the polymerizable monomer is usually 100 or more.

In addition, the oligomeric polymerizable compound (hereinafter, also referred to as a polymerizable oligomer) is typically a polymer having a relatively low molecular weight, and is preferably a polymer formed by bonding 10 to 100 polymerizable monomers. Thing. As the molecular weight, the weight average molecular weight in terms of polystyrene obtained by gel permeation chromatography (GPC) is preferably 2,000 to 20,000, more preferably 2,000 to 15,000, and most preferably 2,000 to 10,000.

The number of functional groups of the polymerizable compound in the present invention refers to the number of polymerizable groups in one molecule.

From the viewpoint of resolvability, the polymerizable compound is preferably a polymerizable compound containing at least one difunctional or higher polymer containing two or more polymerizable groups, and more preferably a polymerizable compound containing at least one trifunctional or higher polymer.

In addition, from the viewpoint that a three-dimensional crosslinked structure can be formed to improve heat resistance, the polymerizable compound in the present invention preferably contains at least one trifunctional or more polymerizable compound. Further, it may be a mixture of a difunctional polymerizable compound or less and a trifunctional polymerizable compound or more.

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 their esters, amidines, and These polymers are preferably esters of an unsaturated carboxylic acid and a polyhydric alcohol compound, amidines of an unsaturated carboxylic acid and a polyamine compound, and these polymers. In addition, an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amine group, or a mercapto group, an addition reaction product with a monofunctional or polyfunctional isocyanate or epoxy, or Dehydration condensation reactants with monofunctional or polyfunctional carboxylic acids. In addition, an unsaturated carboxylic acid ester or amidoamine having an electrophilic substituent such as an isocyanate group or an epoxy group, and an addition reaction product of a monofunctional or polyfunctional alcohol, amine, or thiol, and further having Substituted reactants of unsaturated carboxylic acid esters or amidines having detachable substituents such as halo group or tosylsulfonyloxy group with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. In addition, as another example, a group of compounds substituted with an unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether, or the like may be used instead of the unsaturated carboxylic acid.

Specific examples of the monomer of the ester of a polyol compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetracarboxylic acid. Methylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylol Propane tris (propylene ethoxypropyl) ether, trimethylolethane 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, sorbose Alkyl hexaacrylate, tris (propyleneoxyethyl) isotricyanate, ethylene isocyanate modified ethylene oxide triacrylate, polyester acrylate oligomer, etc.

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

Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, and Methylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetraitaconate, and the like.

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

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

Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate Esters, etc.

As examples of other esters, for example, the aliphatic alcohol-based esters described in Japanese Patent Publication No. 46-27926, Japanese Patent Publication No. 51-47334, and Japanese Patent Publication No. 57-196231 can be suitably used. Or an aromatic skeleton described in Japanese Patent Laid-Open No. 59-5240, Japanese Patent Laid-Open No. 59-5241, and Japanese Patent Laid-Open No. 2-226149, Japanese Patent Laid-Open No. 1-15613 Those containing amine groups described in the publication.

Specific examples of the monomer of a polyamine compound and amidamine of an unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, and 1,6-hexamethylene Bis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriamine triacrylamide, xylylene bisacrylamine, xylylene bismethacrylamine, and the like.

As another example of a preferable amidine-based monomer, those having a cyclohexyl structure described in Japanese Patent Publication No. 54-21726 can be cited.

In addition, a urethane-based addition polymerizable monomer produced by an addition reaction of an isocyanate and a hydroxyl group is also suitable. Examples of such a specific example include those described in Japanese Patent Publication No. 48-41708 A polyisocyanate compound having two or more isocyanate groups in one molecule is obtained by adding two or more polymers in one molecule by adding a hydroxyl group-containing vinyl monomer represented by the following general formula (A). Synthetic vinyl vinyl carbamate compounds and 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 )

In addition, for example, the acrylic urethanes described in Japanese Patent Laid-Open No. 51-37193, Japanese Patent Laid-Open No. 2-32293, Japanese Patent Laid-Open No. 2-16765, or Japanese Patent Laid-Open No. 58 No. -49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, Japanese Patent Publication No. 62-39418, and urethane compounds having an ethylene oxide skeleton The class is also suitable.

In addition, in the present invention, as the polymerizable compound, compounds described in paragraphs 0095 to 0108 of Japanese Patent Application Laid-Open No. 2009-288705 can be suitably used.

In addition, as the polymerizable compound, a compound having a boiling point of 100 ° C. or higher under 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 tetra (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tris (acryloxypropyl) ) Ether, tris (acrylic acid) (Ethyl) isocyanurate, glycerol, or trimethylolethane, etc., are added to polyfunctional alcohols by adding ethylene oxide or propylene oxide, and then (meth) acrylated, such as the Japanese patent The (meth) acrylic acid urethanes described in Japanese Patent Application Publication No. 48-41708, Japanese Patent Application Publication No. 50-6034, and Japanese Patent Application Publication No. 51-37193. Japanese Patent Application Publication No. 48- The polyester acrylates described in JP 64183, JP 49-43191, and JP 52-30490, are epoxy acrylic acid that is a reaction product of epoxy resin and (meth) acrylic acid. Polyfunctional acrylates or methacrylates, such as esters, and mixtures of these. In addition, the compounds described in Japanese Patent Laid-Open No. 2008-292970, paragraphs 0254 to 0257 are also suitable. In addition, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group, such as glycidyl (meth) acrylate, can also be mentioned.

In addition, as other preferable polymerizable compounds, those having a fluorene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and Japanese Patent No. 4364216 can also be used. Cardo resin is a compound containing two or more ethylenically unsaturated groups.

Furthermore, as other examples of the polymerizable compound, specific unsaturated compounds described in Japanese Patent Publication No. 46-43946, Japanese Patent Publication No. 1-40337, and Japanese Patent Publication No. 1-40336 can be cited. Or a vinylphosphonic acid compound described in Japanese Patent Laid-Open No. 2-25493 and the like. In addition, in some cases, a structure containing a perfluoroalkyl group described in Japanese Patent Laid-Open No. 61-22048 is suitably used. Furthermore, you can also use "Japan Adhesive Association Journal" vol.20, No. 7, pages 300 to 308 (1984) are introduced as photocurable monomers and oligomers.

In addition to the above, a polymerizable compound represented by the following general formula (MO-1) to general formula (MO-5) may be suitably used. In the formula, when T is an oxyalkylene group, a carbon atom-side end is bonded to R.

In the general formula, n is an integer from 0 to 14, and m is an integer from 1 to 8. Multiple R and T in one molecule may be the same or different.

In each polymerizable compound represented by the general formula (MO-1) to the general formula (MO-5), at least one of a plurality of Rs is represented by -OC (= O) CH = CH ₂ or- The group represented by OC (= O) C (CH ₃ ) = CH ₂ .

In the present invention, as a specific example of the polymerizable compound represented by the general formula (MO-1) to the general formula (MO-5), a paragraph of Japanese Patent Application Laid-Open No. 2007-269779 may be suitably used. Compounds described in Nos. 0248 to 0251.

In addition, the following compounds described in Japanese Patent Application Laid-Open No. 10-62986 as the general formula (1) and the general formula (2) together with specific examples thereof can also be used as polymerizable compounds. The compounds are used in polyfunctional alcohols. A compound obtained by addition of ethylene oxide or propylene oxide, followed by (meth) acrylic acid esterification.

As the polymerizable compound, dipentaerythritol triacrylate (commercially available) The products sold are KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd., and dipentaerythritol tetraacrylate (commercial products are Kayarad D-320; Nippon Kayaku Co., Ltd. (Manufactured), dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product) It is KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.), and the structure of these (meth) acrylfluorenyl groups via ethylene glycol residues and propylene glycol residues. 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 phosphate group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to have an acid group. The polyfunctional monomer is particularly preferably one in which the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polyacid-modified acrylic oligomers produced by Toa Synthesis Co., Ltd.

The polyfunctional monomer having an acid group may be used alone or in combination of two or more. In addition, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination.

The preferred acid value of the polyfunctional monomer having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, particularly preferably 5 mgKOH / g to 30 mgKOH / g. When the polyvalent monomer has an acid value within the above range, it is excellent in manufacturing or handling properties, and further, it is excellent in developability. 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 trimethylolethane, di-trimethylolethane, and trimethylol. Polyols such as methylpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, and trimethylol melamine are obtained by esterification with (meth) acrylic acid and ε-caprolactone Ε-caprolactone modified polyfunctional (meth) acrylate. Among these, a polymerizable compound having a caprolactone structure represented by the following general formula (B) is preferred.

Formula (B)

(In the formula, 6 Rs are all groups represented by the following general formula (C), or 1 to 5 of 6 Rs are groups represented by the following general formula (C), and the remainder is (The group represented by the following general formula (D))

Formula (C) [Chem. 14]

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 or 2, and "*" represents a bonding bond.)

Formula (D)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.)

Such a polymerizable compound having a caprolactone structure is commercially available, for example, as KAYARAD DPCA series from Nippon Kayakusho Co., Ltd., and examples include DPCA-20 (the general formula (B) to the general formula In (D), m = 1, the number of groups represented by the general formula (C) = 2, and R ¹ is a hydrogen atom compound), DPCA-30 (the general formula (B) to the general formula (D) ), M = 1, the number of groups represented by the general formula (C) = 3, and R ¹ is a hydrogen atom compound), DPCA-60 (in the general formula (B) to general formula (D) , M = 1, the number of groups represented by the general formula (C) = 6, compounds in which R ¹ is a hydrogen atom), DPCA-120 (in the general formula (B) to general formula (D), m = 2, the number of groups represented by the general formula (C) = 6, compounds 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 alone, Or you can mix and use two or more types.

It is also preferable that the polymerizable compound is at least one selected from the group of compounds represented by the following general formula (i) or general formula (ii).

In the general formula (i) and the general formula (ii), E each independently represents-((CH ₂ ) _y CH ₂ O)-, or-((CH ₂ ) _y CH (CH ₃ ) O)-, y, respectively Each independently represents an integer of 0 to 10, and X each independently represents a (meth) acrylfluorenyl group, a hydrogen atom, or a carboxyl group.

In the general formula (i), the total number of (meth) acrylfluorenyl groups is three or four, m each independently represents an integer of 0 to 10, and the total of each m is an integer of 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 number of (meth) acrylfluorenyl groups is five or six, 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 general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.

In addition, 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 general formula (ii), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.

In addition, the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

-((CH ₂ ) _y CH ₂ O)-or-((CH ₂ ) _y CH (CH ₃ ) O)-in the general formula (i) or (ii) is preferably a terminal bond on the oxygen atom side Knot form on X. In particular, in the general formula (ii), it is preferable that all six X's are acrylfluorenyl groups.

The compound represented by the general formula (i) or the general formula (ii) can be synthesized by a step which is a conventionally known step by performing a ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide. A step of bonding a ring-opening skeleton and a step of introducing a (meth) acrylfluorenyl group by reacting a terminal hydroxyl group of the ring-opening skeleton with, for example, (meth) acrylfluorene chloride. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (i) or the general formula (ii).

Among the compounds represented by the general formulae (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferred.

Specifically, compounds represented by the following formulae (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)") are mentioned, and among them, exemplary compounds are preferred. (a), exemplified compound (b), exemplified compound (e), exemplified compound (f).

[Chemical 17]

[Chemical 18]

Examples of commercially available products of the polymerizable compound represented by the general formula (i) and the general formula (ii) include, for example, tetrafunctional acrylic acid having four ethoxyl chains manufactured by Sartomer Corporation. SR-494 of ester, DPCA-60 as a hexafunctional acrylate having 6 pentyloxy chains, and TPA as a trifunctional acrylate having 3 butyloxy groups -330 etc.

Examples of the polymerizable compound include acrylic acid described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765. Urethanes, or Japanese Patent Publication No. 58-49860, Japanese Patent Publication The urethane compounds having an ethylene oxide-based skeleton described in JP 56-17654, JP 62-39417, and JP 62-39418 are also suitable. Furthermore, as the polymerizable compound, JP-A-63-277653, JP-A-63-260909, and JP-A-105238 have amine groups in the molecule. Addition polymerizable monomers having a structure or a thioether group structure.

Examples of commercially available polymerizable compounds include urethane oligomers UAS-10 and UAB-140 (manufactured by Sanyo Kokusaku Pulp), NK ester (NK ESTER) M-40G, NK ester (NK ESTER) 4G, NK ester (NK ESTER) M-9300, NK ester (NK ESTER) A-9300, UA-7200 (made by Shin Nakamura Chemical Co., Ltd.), DPHA-40H (made 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.

* In the formula is a link key.

Specific examples of the polymerizable compound having the partial structure include trimethylolpropane tri (meth) acrylate, ethylene isocyanate modified ethylene oxide di (meth) acrylate, and iso Triethylene cyanocyanate modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, and the like can be used particularly preferably in the present invention.

In the thermosetting resin composition of the present invention, from the viewpoint of good curability and heat resistance, the content of the polymerizable compound is preferably 1% by mass to the total solid content of the thermosetting resin composition. 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 singly or in combination of two or more kinds.

In addition, 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, and most preferably 90 / 10 ~ 50/50. When the mass ratio of the thermosetting resin and the polymerizable compound is within 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 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 that generates radicals by the energy of heat and starts or accelerates the polymerization reaction of the polymerizable compound. By adding a thermal polymerization initiator, when the cyclization reaction of the thermosetting resin proceeds, The polymerization reaction proceeds. In addition, when the thermosetting resin contains an ethylenically unsaturated bond, the cyclization of the thermosetting resin can be performed 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, onium salt compounds, organic peroxides, sulfur compounds, hexaaryl biimidazole compounds, ketoxime ester compounds, borate compounds, azineium compounds, and metallocenes Compounds, active ester compounds, compounds having a carbon halogen bond, azo compounds, and the like. Among these, an organic peroxide or an azo compound is more preferable, and an organic peroxide is particularly preferable.

Specifically, the compounds described in paragraphs 0074 to 0118 of Japanese Patent Laid-Open No. 2008-63554 can be mentioned.

Among 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 0.1% by mass to 50% by mass relative to the total solid content of the thermosetting resin composition. It is preferably 0.1% to 30% by mass, and particularly preferably 0.1% to 20% by mass. Moreover, it is preferable to contain 0.1-50 mass parts of thermal polymerization initiators with respect to 100 mass parts of polymerizable compounds, and it is more preferable to contain 0.5-30 mass parts. According to this aspect, a cured film having more excellent heat resistance is easily formed.

There may be only one thermal polymerization initiator, or two or more. When there are two or more types of thermal polymerization initiators, it is preferable that the total thereof is within the above range.

<< sensitized pigment >>

The thermosetting resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electronically excited state. The sensitized dye in an electronically excited state is brought into contact with a compound represented by the general formula (1), a thermal polymerization initiator, a photopolymerization initiator, and the like, and causes effects such as electron movement, energy movement, and heat generation. Thereby, the compound represented by the general formula (1), the thermal polymerization initiator, and the photopolymerization initiator undergo chemical changes to decompose, and generate radicals, acids, or bases.

As an example of a preferable sensitizing dye, the compounds which belong to the following compounds and which have an absorption wavelength in the 300-450 nm region are mentioned. Examples include polynuclear aromatics (e.g., phenanthrene, anthracene, pyrene, pyrene, triphenylene, 9,10-dialkoxyanthracene), xanthene (e.g., luciferin, eosin, erythrosine, rose Red B, Bengal Rose Red), thiaxanthones, cyanines (e.g., thiocyanocyanine, oxocyanine), merocyanines (e.g., merocyanine, oxocyanine), thiazine (E.g., thizone, methylene blue, toluidine blue), acridines (e.g., acridine orange, chloroflavin, acridine xanthophylls), anthraquinones (e.g., anthraquinone), and squaronium salts ( (E.g. lactonium salt), coumarins (e.g. 7-diethylamino-4-methylcoumarin), phenothiazines, styrylbenzenes, distyrylbenzenes And carbazoles.

Among them, in the present invention, from the viewpoint of the starting efficiency, it is preferably used in combination with polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, pyrene, triphenylene), thioanthrones, and distyrylbenzenes. It is more preferable to use a compound having an anthracene skeleton in combination with styrylbenzenes. Particularly preferred specific compounds include 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and the like.

When the thermosetting resin composition of the present invention contains a sensitizing dye, it is relatively For the total solid content of the thermosetting resin composition, the content of the sensitizing dye is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 15% by mass, and even more preferably 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 present invention may contain a photopolymerization initiator. Since the thermosetting resin composition of the present invention contains a photopolymerization initiator, after the thermosetting resin composition is applied to a semiconductor wafer or the like to form a layered composition layer, light is radiated to generate free radicals. Or the hardening by an acid can reduce the solubility in a light irradiation part. Therefore, for example, by exposing the composition layer through a photomask having a pattern covering only the electrode portion, there is an advantage that regions having different solubility can be easily produced according to the pattern of the electrode.

The photopolymerization initiator is not particularly limited as long as it has the ability to start the polymerization reaction (crosslinking reaction) of the polymerizable compound, and it can be appropriately selected from known photopolymerization initiators. For example, it is preferable to have sensitivity in the ultraviolet region to visible rays. In addition, it may be an active agent that generates an active radical by having a certain effect with a photo-excited sensitizer.

The photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in a range of about 300 nm to 800 nm (preferably 330 nm to 500 nm). The Mohr absorption coefficient of a compound can be measured using a known method, and specifically, for example, it is preferably a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian). (spectrophotometer)), and the measurement was performed at a concentration of 0.01 g / L using an ethyl acetate solvent.

As the photopolymerization initiator, a known compound can be used without limitation, and examples thereof include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group), and fluorenyl groups. Phosphonium compounds such as phosphine oxide, oxime compounds such as hexaaryl biimidazole, oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxybenzene Ethyl ketone, azo-based compounds, azide-based compounds, metallocene compounds, organic boron compounds, iron aromatic hydrocarbon complexes, and the like.

As a halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., A compound described in "Bull. Chem. Soc. Japan", 42, 2924 (1969), and described in British Patent No. 1348492. Compounds, compounds described in Japanese Patent Laid-Open No. 53-133428, compounds described in German Patent No. 3337024, FC Schaefer and other "J. Org. Chem.", 29 The compound described in 1527 (1964), the compound described in Japanese Patent Laid-Open No. 62-58241, the compound described in Japanese Patent Laid-Open No. 5-281728, the compound described in Japanese Patent Laid-Open No. 5-34920, United States of America Compound described in Patent No. 4212976 and the like.

Examples of the compounds described in the specification of US Patent No. 4212976 include compounds having an oxadiazole skeleton (for example, 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-tri Bromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl Methyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3 , 4-oxadiazole, 2-tribromomethyl-5-styryl-1,3,4-oxadiazole, etc.).

Examples of the photopolymerization initiator other than the above include acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9'-acridyl) heptane, etc.), N -Phenylglycine, etc., polyhalogen compounds (e.g. carbon tetrabromide, phenyltribromomethylphosphonium, phenyltrichloromethylketone, etc.), coumarins (e.g. 3- (2-benzofuran (Fluorenyl) -7-diethylaminocoumarin, 3- (2-benzofuranmethylfluorenyl) -7- (1-pyrrolidinyl) coumarin, 3-benzylfluorenyl-7- Diethylaminocoumarin, 3- (2-methoxybenzylidene) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzylidene)- 7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin Coumarin), 3-benzyl-7-methoxycoumarin, 3- (2-furanmethyl) -7-diethylaminocoumarin, 3- (4-diethyl Amine cinnamyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzyl-5,7-dipropyl Oxycoumarin, 7-benzotriazol-2-ylcoumarin, Japanese Patent Laid-Open No. 5-19475, Japanese Patent Laid-Open No. 7-271028 Coumarin compounds described in Japanese Patent Laid-Open No. 2002-363206, Japanese Patent Laid-Open No. 2002-363207, Japanese Patent Laid-Open No. 2002-363208, Japanese Patent Laid-Open No. 2002-363209, and the like ), Fluorenyl phosphine oxides (e.g. bis (2,4,6-trimethylbenzyl))-phenyl Phosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes ( For example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, η5-cyclopentadiene Alkenyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), Japanese Patent Laid-Open No. 53-133428, Japanese Patent Laid-Open No. 57-1819, Japanese Patent No. Compounds described in Japanese Patent Publication No. 57-6096 and U.S. Patent No. 3615455.

Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, benzophenonetetracarboxylic acid Or its tetramethyl ester, 4,4'-bis (dialkylamino) benzophenones (e.g. 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (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, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthrenequinone, xanthone, thiathrone, 2-chloro-thiathrone , 2,4-diethylthiaxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinylphenyl) -1-butanone, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholinyl-1-acetone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomerization Thing , Benzoin, benzoin ethers (e.g. benzoin methyl ether, benzoin ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloroacridone, N-methyl Acridinone, N-butylacridone, N-butyl-chloroacridone, and the like.

Among commercially available products, Kayacure DETX (manufactured by Nippon Kayaku) can also be suitably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a fluorenylphosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Laid-Open No. 10-291969 and a fluorenylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used. .

As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IGACURE can be used. Solid (IRGACURE) -127 (trade name: all manufactured by BASF).

As the aminoacetophenone-based initiator, commercially available products, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: both) (Manufactured by BASF).

As the aminoacetophenone-based initiator, a compound described in Japanese Patent Laid-Open No. 2009-191179 can be used in which the absorption wavelength matches a long-wave light source such as 365 nm or 405 nm.

As a fluorenylphosphine-based initiator, commercially available products IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF) can be used.

The photopolymerization initiator is more preferably an oxime-based compound. As a specific example of the oxime-based initiator, the one described in Japanese Patent Laid-Open No. 2001-233842 can be used. A compound, a compound described in Japanese Patent Laid-Open No. 2000-80068, and a compound described in Japanese Patent Laid-Open No. 2006-342166.

Preferred oxime compounds include, for example, 3-benzyloxyiminobutane-2-one, 3-ethylamidooxyiminobutane-2-one, and 3-propanyloxy Iminobutane-2-one, 2-acetamidoiminopentane-3-one, 2-acetamidoimino-1-phenylpropane-1-one, 2-benzyl Ethoxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino -1-phenylpropane-1-one and the like.

Examples of the oxime compounds include: "The Journal of the British Chemical Society, JCS Perkin II" (1979) pp.1653-1660, "The Journal of the British Chemical Society, Perkin Journal II" (1979 Pp. 156-162, "Journal of Photopolymer Science and Technology" (1995) pp. 202-232, compounds described in Japanese Patent Laid-Open No. 2000-66385, Japanese patents The compounds described in each publication of JP-A-2000-80068, JP-A-2004-534797, and JP-A-2006-342166.

Commercially available products can also use IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA).

In addition, the compound described in Japanese Patent Publication No. 2009-519904, in which an oxime is linked to the N-position of carbazole, and US Pat. No. 7,626,957, in which a hetero substituent is introduced into a benzophenone moiety, can also be used. Compounds, pigment parts The compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, and the ketoxime-based compounds described in International Publication No. 2009-131189, in which a nitro group is introduced, contain a triazine in the same molecule. The compounds described in U.S. Patent No. 7,565,910 for the skeleton and the oxime skeleton, and the compounds described in Japanese Patent Laid-Open No. 2009-221114, which have the maximum absorption at 405 nm and have good sensitivity to a g-ray light source.

In addition, cyclic oxime compounds described in Japanese Patent Laid-Open No. 2007-231000 and Japanese Patent Laid-Open No. 2007-322744 can also be suitably used. Among the cyclic oxime compounds, in particular, the cyclic oxime compound condensed in a carbazole pigment described in Japanese Patent Laid-Open No. 2010-32985 and Japanese Patent Laid-Open No. 2010-185072 has high light absorption, It is preferable from the viewpoint of high sensitivity.

In addition, a compound described in Japanese Patent Laid-Open No. 2009-242469, which is a compound having an unsaturated bond at a specific site of an oxime compound, can also be suitably used.

The most preferable oxime compound includes an oxime compound having a specific substituent shown in Japanese Patent Laid-Open No. 2007-269779, or an oxime having a thioaryl group shown in Japanese Patent Laid-Open No. 2009-191061. Compounds etc.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, and fluorenyl groups. Phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene -Benzene-iron complex Compounds in the group consisting of compounds and their salts, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.

More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, fluorenylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds. Particularly preferred is at least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-amino ketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound, and most preferably Use oxime compounds.

In addition, as the photopolymerization initiator, a compound that generates an acid having a pKa of 4 or less can be preferably used, and a compound that generates an acid having a pKa of 3 or less is more preferable.

Examples of the acid-generating compounds include trichloromethyl-mesytriazines, sulfonium or sulfonium salts, quaternary ammonium salts, diazomethane compounds, sulfonium imine sulfonate compounds, and oxime sulfonic acids Ester compounds, etc. Among these, from the viewpoint of high sensitivity, it is preferable to use an oxime sulfonate compound. These acid generators may be used alone or in combination of two or more.

Specifically, the acid generator described in paragraph number [0073] to paragraph number [0095] of Japanese Patent Laid-Open No. 2012-8223 can be cited.

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, and more preferably from 0.1% by mass relative to the total solid content of the thermosetting resin composition. Mass% to 20% by mass, and more preferably 0.1% to 10% by mass. The content of the photopolymerizable initiator is preferably 1 to 20 parts by mass, and more preferably 3 parts by mass based on 100 parts by mass of the polymerizable compound. ~ 10 parts by mass.

The photopolymerization initiator may be only one type, or two or more types. When there are two or more kinds of photopolymerization initiators, it is preferable that the total thereof is within the above range.

<< chain transfer agent >>

The thermosetting resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule can be used. These chain transfer agents provide hydrogen to low-activity free radical species to generate free radicals, or are deprotonated after being oxidized, thereby generating free radicals. In particular, thiol compounds (e.g., 2-mercaptobenzimidazoles, 2-mercaptobenzothiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles) can be preferably used. Wait).

When the thermosetting resin composition contains a chain transfer agent, the preferable content of the chain transfer agent is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total solid content of the thermosetting resin composition, and more preferably It is 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass.

The chain transfer agent may be only one kind, or two or more kinds. When there are two or more kinds of chain transfer agents, it is preferable that the total thereof is within the above range.

<< polymerization inhibitor >>

In order to prevent unnecessary thermal polymerization of the thermosetting resin and the polymerizable compound during manufacturing or storage, it is preferable to add a small amount of a polymerization inhibitor to the thermosetting resin composition of the present invention.

Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-third-butyl-p-cresol, gallophenol, third-butylcatechol, benzoquinone, and 4,4. '-Thiobis (3-methyl-6-third butylphenol), 2,2'-methylenebis (4-methyl-6-third 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 relative to the total solid content of the thermosetting resin composition.

There may be only one polymerization inhibitor, or two or more. When there are two or more kinds of polymerization inhibitors, it is preferable that the total thereof is within the above range.

<< Higher fatty acid derivatives etc. >>

In the thermosetting resin composition of the present invention, in order to prevent polymerization from being hindered by oxygen, a higher fatty acid derivative such as behenic acid or behenamine may be added and applied to the coating. During the subsequent drying process, the surface of the thermosetting resin composition is biased.

When the thermosetting resin composition contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1% by mass to 10% by mass based on the total solid content of the thermosetting resin composition.

The higher fatty acid derivative and the like may be only one kind, or two or more kinds. When there are two or more types of higher fatty acid derivatives, it is preferable that the total is within the above range.

<< Solvent >>

When the thermosetting resin composition of the present invention is formed into a layer by coating, it is preferable to prepare a solvent. As long as the thermosetting resin composition can be formed into a layer, The solvent can be used by a publicly known one without limitation.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl acetate. Butyl acid ester, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl oxyacetate (for example: methyl oxyacetate, ethyl oxyacetate Butyl oxyacetate (e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-oxyl Alkyl propionates (e.g. methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g. methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 -Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), alkyl 2-oxypropionate (for example: methyl 2-oxypropionate, 2-oxypropionate Ethyl ester, propyl 2-oxypropionate, etc. (e.g. methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-ethoxypropionate Acid methyl ester, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g. 2-methyl Methyloxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methylpyruvate, ethylpyruvate, propylpyruvate, methylacetate, Ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc., and examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, and ethylene glycol monobasic. Methyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl 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, and the like, and examples of the ketones include methyl ethyl ketone, cyclohexanone, Cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and, as aromatic Examples of the aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like. Examples of the sulfenes include dimethyl sulfene.

From the viewpoint of improving the coating surface state and the like, a form in which two or more solvents are mixed is also preferable. In this case, it is particularly preferable that the mixed solution contains a material selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, and ethyl lactate. Ester, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfene, ethyl Two or more of carbitol 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 becomes 5 to 80% by mass from the viewpoint of coating properties. More preferably, the total solid content concentration of the thermosetting resin composition is 5 to 70% by mass, and particularly preferably the total solid content concentration of the thermosetting resin composition is 10 to 60% by mass. Amount of%.

The solvent may be only one kind, or two or more kinds. When there are two or more solvents, it is preferable that the total thereof is within the above range.

<< Interactive Agent >>

To the thermosetting resin composition of the present invention, from the viewpoint of further improving the coating property, various surfactants may be added. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.

In particular, by containing a fluorine-based surfactant, the liquid characteristics (especially fluidity) when the coating liquid is prepared are further improved, so that the uniformity of the coating thickness or the liquid saving property can be further improved.

When a coating liquid containing a fluorine-based surfactant is used to form a film, the interfacial tension between the surface to be coated and the coating liquid is reduced, whereby the wettability to the surface to be coated is improved, and to the surface to be coated Surface coating properties are improved. Therefore, it is effective from the viewpoint that a thin film having a small thickness and a uniform thickness can be formed more suitably even when a thin film of about several μm is formed with a small amount of liquid.

The fluorine content of the fluorine-based surfactant is preferably 3% to 40% by mass, more preferably 5% to 30% by mass, and particularly preferably 7% to 25% by mass. A fluorine-based surfactant having a fluorine content ratio within this range is effective from the viewpoint of the uniformity of the thickness of the coating film or the liquid saving property, and also has good solubility.

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, manufactured by DIC (shares)), Fluorad FC430 Fluorad FC431, Fluorad FC171 (above, made by Sumitomo 3M), Safron (Surflon) S-382, Surflon SC-101, Surflon SC-103, Surflon SC-104, Surflon SC-105, Shaflon (Surflon) SC1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above, manufactured by Asahi Glass (Stock)) ), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.

Specific examples of the non-ionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates such as glycerol propoxylate, Glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylen Glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L 10 manufactured by BASF, Pluronic L 31, General Pluronic L61, Pluronic L62, Pluronic 10R5, Pluronic 17R2, Pluronic 25R2, Tetronic 304 , Tetronic 701, Tetronic 704, Tetronic 901, Tetronic 904, Tetronic 150R1), Solosperse 20000 (Lubrizol Japan) (Lubrizol) (manufactured)) and so on.

Specific examples of the cationic surfactant include a phthalocyanine derivative (trade name: Efka (EFKA) -745, manufactured by Morishita Industries, Ltd.), and an organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) (Manufacturing), (meth) Acrylic (co) polymers Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yushang Co., Ltd.), etc.

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

Examples of the silicone-based surfactant include Toray. `` Toray Silicone DC3PA '', `` Toray Silicone SH7PA '', `` Toray Silicone DC11PA '', `` Toray Silicone '' manufactured by Dow Corning ) SH21PA "," Toray Silicone SH28PA "," Toray Silicone SH29PA "," Toray Silicone SH30PA "," Toray Silicone SH8400 " "," TSF-4440 "," TSF-4300 "," TSF-4445 "," TSF-4460 "," TSF-4452 "manufactured by Momentive Performance Materials, and Shinetsu silicone ) "KP341", "KF6001", "KF6002" manufactured by Co., Ltd., "BYK307", "BYK323", "BYK330", etc. manufactured by BYK Chemie.

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, relative to the total solid content of the thermosetting resin composition. quality%.

The surfactant may be only one kind, or two or more kinds. When there are two or more kinds of surfactants, it is preferable that the total thereof is within the above range.

<< Other additives >>

To the extent that the effects of the present invention are not impaired, the thermosetting resin composition in the present invention may be optionally blended with various additives such as a hardener, a hardening catalyst, a silane coupling agent, a filler, an adhesion promoter, an antioxidant, UV absorber, anti-agglomerating agent, anti-corrosive agent, etc. When these additives are blended, the total blended amount 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 respective components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

<Application of thermosetting resin composition>

Since the thermosetting resin composition of the present invention can form a cured film excellent in heat resistance and insulation, it can be preferably used for an insulating film of a semiconductor element, an interlayer insulating film for rewiring, and the like. In particular, it can be preferably used for an interlayer insulating film for rewiring in a three-dimensional mounting element.

It can also be used for photoresists (galvanic resist, etching resist, solder top resist) and the like for electronics.

In addition, it can also be used for the production of layouts such as lithographic layouts and screen layouts. For the use of etching of formed parts, electronics, especially the production of protective coatings and dielectric layers in microelectronics, etc.

<Method for Forming Hardened Film>

Next, a method for forming a cured film of the present invention will be described.

A method for forming a cured film of the present invention includes: applying the thermosetting resin of the present invention A step of applying the composition to the substrate, and a step of curing the thermosetting resin composition corresponding to the substrate.

<< Procedure for applying thermosetting resin composition to substrate >>

Examples of the application method of the thermosetting resin composition onto the substrate include spinning, dipping, doctor blade coating, suspended casting, coating, spraying, electrostatic spraying, and reverse roll coating. For reasons of uniform application to a substrate, electrostatic spraying and reverse roll coating are preferred. For example, the photosensitive layer may be introduced onto a temporary flexible carrier, such as a copper film printed circuit board using layer movement caused by lamination, and then coated on 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, silicon, silicon nitride, and a composite substrate obtained by vapor-depositing molybdenum, titanium, aluminum, copper, or the like on these substrates.

Examples include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polyfluorene, and polyether. Samarium, Polyarylate, Allyl Diethylene Glycol Carbonate, Polyfluorene, Polyfluorene, Polyfluorene, Imine, Polyether, Polyimide, Polybenzoxazole, Polyphenylene Sulfide, Polycycloolefin Fluorine resins such as norbornene resin, polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, silicone resins, ionic polymer resins, cyanate resins, crosslinked fumarate diesters, Synthetic resins such as cyclic polyolefin, aromatic ether, maleimide-olefin, cellulose, episulfide compounds, etc. are used as the substrate of the resin. These substrates are rarely used directly in the above-mentioned form. Usually, according to the form of the final product, for example, a multilayer build-up such as a thin film transistor (TFT) device is formed. structure.

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

The thermosetting resin composition is preferably applied to a substrate and then dried. The drying is preferably performed at 60 ° C. to 150 ° C. for 10 seconds to 2 minutes.

<< Heating step >>

By heating the thermosetting resin composition applied to the substrate, the thermosetting resin undergoes a cyclization reaction, and a cured film having excellent heat resistance can be formed.

The heating temperature is preferably 50 ° C to 300 ° C, more preferably 100 ° C to 200 ° C, and particularly preferably 100 ° C to 180 ° C.

According to the present invention, the amine species generated from the compound represented by the general formula (1) functions as a catalyst for the cyclization reaction of the thermosetting resin, and can promote the cyclization reaction of the thermosetting resin. The cyclization reaction of the thermosetting resin proceeds at a low temperature. Therefore, a cured film excellent in heat resistance can be formed even at a low temperature treatment of 200 ° C or lower.

In the present invention, a pattern forming step may be performed between the step of applying the thermosetting resin composition on a substrate and the heating step. The pattern forming step can be performed by, for example, a photolithography method. For example, the method performed through the exposure process and the process of performing a development process is mentioned. A case where a pattern is formed by a photolithography method will be described.

<< Exposure steps >>

In the exposure step, actinic radiation or radiation in a predetermined pattern is irradiated in accordance with the thermosetting resin composition used on the substrate.

The wavelength of actinic rays or radiation varies depending on the composition of the thermosetting resin composition, but is preferably 200 nm to 600 nm, and more preferably 300 nm to 450 nm.

As a 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 (Light Emitting Diode, LED) light source, an excimer laser generating device, etc. can be used, and an i-ray (365 nm), Actinic rays having wavelengths of 300 nm to 450 nm, such as h-rays (405 nm) and g-rays (436 nm). In addition, the irradiated light may be adjusted by a spectroscopic filter such as a long-wavelength cut-off filter, a short-wavelength cut-off filter, or a band-pass filter, if necessary. The exposure amount is preferably 1 mJ / cm ² to 500 mJ / cm ² .

As the exposure device, various methods such as mirror projection aligner, stepper, scanner, proximity type, contact type, micro lens array type, lens scanner type, and laser exposure type can be used. Exposure machine.

Furthermore, the photopolymerization of (meth) acrylates and similar olefinically unsaturated compounds is well known, and especially in thin layers is prevented by oxygen in the air. This effect can be mitigated, for example, by a known prior method such as temporary introduction of a film layer of polyvinyl alcohol, or front exposure or front adjustment in an inert gas.

<< Steps for Developing Process >>

In the step of performing the development treatment, the unexposed portion of the thermosetting resin composition is developed using a developing solution. As the developing solution, aqueous alkaline development can be used Liquid, organic solvents, etc.

Examples of the alkaline compound used in the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, and metasilicon. Sodium, potassium metasilicate, ammonia or amines. 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 these, a metal-free basic compound is preferred. A suitable aqueous alkaline developer is usually alkali to 0.5N, but it may be appropriately diluted before use. For example, an aqueous alkaline developing solution of about 0.15N to 0.4N, preferably 0.20N to 0.35N is also suitable. The basic compound may be only one kind, or two or more kinds. When there are two or more kinds of basic compounds, it is preferable that the total thereof is within the above range.

As the organic solvent, the same solvents as those used for the thermosetting resin composition can be used.

In a field to which the method for forming a cured film of 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, and the like. In particular, since it has good resolvability, it can be preferably used for an interlayer insulating film for rewiring in a three-dimensional mounting element.

It can also be used for photoresists (galvanic resist, etching resist, solder top resist) and the like for electronics.

In addition, it can also be used in the production of lithographic layouts or screen layouts. The use of etching of shaped parts, electronics, especially protective coatings in microelectronics and the manufacture of dielectric layers.

<Semiconductor element>

Next, an embodiment of a semiconductor element using the thermosetting resin composition of the present invention 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 multilayer body 101 in which a plurality of semiconductor devices (semiconductor wafers) 101 a to 101 d are stacked is arranged on a wiring substrate 120.

In addition, in this embodiment, the case where the number of stacked layers of a semiconductor device (semiconductor wafer) is four is described, but the number of stacked layers of a semiconductor device (semiconductor wafer) is not particularly limited, and may be, for example, two layers, 8 layers, 16 layers, 32 layers, etc. Alternatively, it may be a single layer.

Each of the plurality of semiconductor devices 101a to 101d includes a semiconductor wafer such as a silicon 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 devices 101 b to 101 d include penetration electrodes 102 b to 102 d, and connection pads (not shown) integrally provided on the penetration electrodes are provided on both surfaces of each semiconductor device.

The laminated body 101 has a structure in which a semiconductor device 101a not having a penetrating electrode and a semiconductor device 101b to a semiconductor device 101d having a penetrating electrode 102b to a pendant electrode 102d are connected by flip chip bonding.

That is, the electrode pads of the semiconductor device 101a without the penetration electrode and the connection pads on the semiconductor device 101a side of the semiconductor device 101b with the penetration electrode 102b adjacent thereto are connected by metal bumps 103a such as solder bumps and have penetrations. The connection pad on the other side of the semiconductor device 101b of the electrode 102b and the connection pad on the semiconductor device 101b side 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 penetrating electrode 102c and the connection pad on the semiconductor device 101c side of the semiconductor device 101d having the penetrating electrode 102d adjacent thereto are connected to a metal bump 103c such as a solder bump. To connect.

An 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 substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring substrate 120 to which a resin substrate is applied include a multilayer copper-clad laminated board (multilayer printed wiring board) and the like.

A surface electrode 120 a is provided on one surface of the wiring substrate 120.

An insulating layer 115 on which the redistribution layer 105 is formed is disposed between the wiring substrate 120 and the multilayer body 101, and the wiring substrate 120 and the multilayer body 101 are electrically connected via the redistribution layer 105. The insulating layer 115 is formed using the thermosetting resin composition of the present invention.

That is, one end of the redistribution layer 105 passes through a metal bump 103d such as a solder bump, and It is connected to the electrode pad formed on the surface of the redistribution layer 105 side of the semiconductor device 101d. The other end of the redistribution layer 105 is connected to the surface electrode 120 a of the wiring substrate via a metal bump 103 e such as a solder bump.

An underfill layer 110 a is formed between the insulating layer 115 and the laminated body 101. An underfill layer 110 b is formed between the insulating layer 115 and the wiring substrate 120.

[Example]

Hereinafter, the present invention will be described more specifically with reference to the examples. However, the present invention is not limited to the following examples as long as the present invention does not exceed the gist thereof. In addition, unless otherwise specified in advance, "%" and "part" are quality standards.

(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-shaped flask, and stirred at 5 ° C or lower for 5 minutes. 23 mmol of sodium hydroxide was added, and 23 mmol of chloroacetic acid was added dropwise. The corresponding arylamine or allylamine was added dropwise at 10 mmol, and 4.6 mmol of potassium iodide was added. The temperature was raised to 90 ° C and stirred for 5 hours. After leaving to cool to room temperature, the precipitated solid was filtered. The obtained solid was reslurried in 2 ml of water, and then air-dried to obtain a target substance.

(Synthesis example of comparative compound) [X-7, X-8]

5 ml of water, 10 mmol of aniline and 10 mmol of glutaric acid or maleic acid were added to a 50 ml eggplant-shaped flask and stirred for 5 minutes. 23 millimoles of sodium hydroxide was added, and heating was continued at 100 ° C for 24 hours. After leaving to cool to room temperature, the precipitated solid was filtered. Reslurry the obtained solid in 2 ml of water Material, and then air-dried to obtain the target.

(Synthesis Example 1) [Polyimide precursor resin (B-1; polyethylenimine precursor resin derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and 3-hydroxybenzyl alcohol) Synthesis of polyimide precursor resin)

14.06 g (64.5 mmol) of pyromellitic dianhydride (drying at 140 ° C for 12 hours) and 16.33 g (131.58 mmol) of 3-hydroxybenzyl alcohol were suspended in 50 ml of N-methylpyrrole Pyridone and dried using a molecular sieve. The suspension was heated at 100 ° C for 3 hours. A clear solution was obtained after several 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, and while maintaining the temperature at -10 ° C ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over a period of 10 minutes. During the period when SOCl ₂ was added, the viscosity increased. After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, at 20 ° C to 23 ° C, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine dissolved in 100 ml of N-methylpyrrolidone was dropped for 20 minutes. Add to the reaction mixture. Then, the reaction mixture was stirred at room temperature overnight. Next, the polyimide precursor resin was precipitated in 5 liters of water, and the water-polyimide precursor resin mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor resin was filtered and removed, and stirred in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45 ° C. for 3 days under reduced pressure.

(Synthesis Example 2) [derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and Synthesis of benzyl alcohol polyimide precursor resin (B-2; polyimide precursor resin without ethylenically unsaturated bonds)

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-methylpyrrolidone And use molecular sieves for drying. The suspension was heated at 100 ° C for 3 hours. A clear solution was obtained after several 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, and while maintaining the temperature at -10 ° C ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over a period of 10 minutes. During the period when SOCl ₂ was added, the viscosity increased. After dilution with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, at 20 ° C to 23 ° C, a solution of 11.08 g (58.7 mmol) of 4,4'-oxydiphenylamine dissolved in 100 ml of N-methylpyrrolidone was dropped for 20 minutes. Add to the reaction mixture. Then, the reaction mixture was stirred at room temperature overnight. Next, the polyimide precursor resin was precipitated in 5 liters of water, and the water-polyimide precursor resin mixture was stirred at 5000 rpm for 15 minutes. The polyimide precursor resin was filtered and removed, and stirred in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried at 45 ° C. for 3 days under reduced pressure.

(Synthesis Example 3) [Polyimide precursor resin (B-3; having ethylenic unsaturation derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, and 2-hydroxyethyl methacrylate) Synthesis of polyimide precursor resin)

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of terephthalic acid Phenol, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was chlorinated with SOCl ₂ and then converted to a polyfluorene imide precursor resin by 4,4'-oxydiphenylamine in the same manner as in Synthesis Example 1. A polyimide precursor resin was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 4) [Polyimide precursor resin (B-4 from pyromellitic dianhydride, 4,4'-oxydiphenylamine, 3-hydroxybenzyl alcohol, and 2-hydroxyethyl methacrylate) ; Synthesis of polyfluorene imide precursor resin with ethylenically unsaturated bonds)

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of terephthalic acid Phenol, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate.

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-formaldehyde. In the pyrrolidone, a molecular sieve is used for drying, and then the suspension is heated at 100 ° C. for 3 hours to produce a diester of pyromellitic acid and 3-hydroxybenzyl alcohol.

The chlorination was carried out with an isomolar mixture of a diester of pyromellitic acid and 2-hydroxyethyl methacrylate and a diester of pyromellitic acid and 3-hydroxybenzyl alcohol using SOCl ₂ to synthesize with a synthesis example. 1 In the same method, 4,4'-oxydiphenylamine was converted into a polyfluorene imide precursor resin, and a polyfluorene imide precursor resin was obtained in the same manner as in Synthesis Example 1.

(Synthesis Example 5) [Polyimide precursor resin (B-5; ethylene derived from pyromellitic dianhydride, 4,4'-oxydiphenylamine, benzyl alcohol, and 2-hydroxyethyl methacrylate) Synthesis of Polyunsaturated Polyimide Precursor Resin)

14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of terephthalic acid Phenol, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic 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-methylpyrrolidine. In the ketone, after drying with a molecular sieve, the suspension was heated at 100 ° C. for 3 hours to produce a diester of pyromellitic acid and benzyl alcohol.

After the chlorination of an equimolar mixture of a diester of pyromellitic acid and 2-hydroxyethyl methacrylate and a diester of pyromellitic acid and benzyl alcohol by SOCl ₂ , the same as in Synthesis Example 1 was obtained. In the method, 4,4'-oxydiphenylamine was converted into a polyfluorene imide precursor resin, and a polyfluorene imide precursor resin was obtained in the same manner as in Synthesis Example 1.

<Alkali production temperature>

Using differential scanning calorimetry (manufactured by Q2000 TA) in pressure-resistant capsules The specific compound (A) was heated to 250 ° C. at 5 ° C./min, the peak temperature of the exothermic peak having the lowest temperature was read, and 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 for a thermosetting resin composition.

<Composition of thermosetting resin composition>

(A) Specific compound: Mass% listed in Table 1

(B) Polyimide precursor resin: mass% described in Table 1

(C) Polymerizable compound: Mass% described in Table 1

(D) Thermal polymerization initiator: Mass% described in Table 1

(Other ingredients)

γ-butyrolactone: 60% by mass

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

[Example 21]

<Composition of thermosetting resin composition>

(A) Specific compound: Mass% listed in Table 1

(B) Polyimide precursor resin: mass% described in Table 1

(C) Polymerizable compound: Mass% described in Table 1

(E) Photopolymerization initiator: mass% described in Table 1

(Other ingredients)

γ-butyrolactone: 60% by mass

The thermosetting resin composition was passed through a filter having a pore width of 0.8 μm and subjected to pressure filtration, and then applied by spin coating (3500 rpm, 30 seconds) on a silicon wafer. The silicon wafer to which the thermosetting resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform film having a thickness of 10 μm was formed on the silicon wafer. An aligner (Karl-Suss MA150) was used to 500 mJ / cm ² for exposure. The exposure was performed using a high-pressure mercury lamp, and the exposure energy at a wavelength of 365 nm was measured.

<Evaluation>

[Sclerosis]

The thermosetting resin composition was passed through a filter having a pore width of 0.8 μm and subjected to pressure filtration, and then applied by spin coating on a silicon wafer (1200 rpm, 30 seconds). The silicon wafer to which the thermosetting resin composition was applied was dried on a hot plate at 100 ° C. for 5 minutes, and a uniform film having a thickness of 10 μm was formed on the silicon wafer.

The film was stripped from a silicon wafer, and thermogravimetric analysis (Thermal Gravimetric Analysis (TGA) measurement) was performed in a state maintained at 250 ° C in nitrogen, and the cyclization time was evaluated. Since the polyfluorene imide precursor resin undergoes a cyclization reaction, mass reduction occurs. Therefore, the time until the mass reduction does not occur is evaluated by the following criteria. The shorter the time, the faster the cyclization speed becomes, and the better the result is.

A: More than 10 minutes and less than 30 minutes

B: More than 30 minutes and less than 60 minutes

C: More than 60 minutes and less than 120 minutes

D: Over 200 minutes. Alternatively, no cyclization was performed.

[stability]

After the thermosetting resin composition was prepared, a container containing 10 g of the thermosetting resin composition was hermetically sealed, and left to stand in an environment of 25 ° C. and 65% humidity. The stability was evaluated by the time until the thermosetting resin composition was cyclized and solids were precipitated. The longer the time, the higher the stability of the composition and the better the result. The precipitation of solids was performed by filtering through a mesh having a pore size of 0.8 μm, and visually observing the presence or absence of mesh-like foreign matter.

A: No solid precipitation was observed even after 30 days

B: Precipitation of solids within 20 or 30 days

C: Precipitation of solids within 10 days and 20 days

D: Solid precipitation within 5 days and 10 days

E: solids precipitated within 5 days

[Heat resistance]

The film was peeled from the silicon wafer, and thermogravimetric analysis (TGA measurement) was performed in a state of being maintained at 350 ° C. for 3 hours in nitrogen, 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 and the better the result. As a result of the evaluation, A to C are preferred from a practical standpoint.

A: 1% by mass or less

B: more than 1% by mass and 5% by mass or less

C: More than 5 mass% and 10 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 hardenability and stability.

In contrast, the thermosetting resin compositions of Comparative Examples 1 to 9 are inferior to at least one of the curability and stability of the thermosetting resin composition of the examples.

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 compounds): the following structure (wherein Me represents a methyl group).

(B) Polyimide precursor resin

B-1 ~ B-5: Polyimide precursor resin B-1 ~ Polyimide precursor resin B-5 synthesized in Synthesis Examples 1 to 5

(C) Polymerizable compound

C-1: NK ester (NK ESTER) M-40G (manufactured by Shin Nakamura Chemical Industry Co., Ltd., monofunctional methacrylate, the following structure)

C-2: NK ester (NK ESTER) 4G (manufactured by Shin Nakamura Chemical Industry Co., Ltd., difunctional methacrylate, the following structure)

C-3: NK ester (NK ESTER) A-9300 (manufactured by Shin Nakamura Chemical Industry Co., Ltd., trifunctional acrylate, the following structure)

(D) Thermal polymerization initiator

D-1: Perbutyl Z (manufactured by Nippon Oil Co., Ltd., third butyl peroxide benzoate, decomposition temperature (10-hour half-life temperature = 104 ° C))

(E) Photopolymerization initiator

E-1: IRGACURE OXE-01 (manufactured by BASF)

<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 applied by spin coating (3500 rpm, 30 seconds) on a resin substrate on which a copper thin layer was formed. The thermosetting resin composition applied to the resin substrate was dried at 100 ° C for 5 minutes.

Then, it heated at 180 degreeC for 20 minutes. In this way, an interlayer insulating film for redistribution is formed.

This interlayer insulating film for rewiring is excellent in insulation.

In addition, as a result of manufacturing a semiconductor element using this interlayer insulating film for rewiring, it was confirmed that the operation was performed without problems.

Furthermore, the same effect can be obtained even if the polyfluorene imine precursor resin is changed to a polyfluorene imine precursor resin and a polybenzoxazole precursor.

Claims (14)

A thermosetting resin composition comprising a compound represented by the following general formula (1) and a thermosetting resin that is cyclized with a base and hardened; In the general 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, m represents an integer of 1 or more, and n Represents an integer of 1 or more, and p represents an integer of 1 or more. The thermosetting resin composition according to item 1 of the scope of patent application, wherein in the general formula (1), A is an aromatic ring group. The thermosetting resin composition according to claim 1 or claim 2, wherein in the general formula (1), A is a benzene ring. The thermosetting resin composition according to claim 1 or claim 2, wherein in the general formula (1), L ¹ and L ² are each independently an alkylene group. The thermosetting resin composition according to item 1 or item 2 of the patent application scope, wherein m, n, and p are 1 in the general formula (1), respectively. The thermosetting resin composition according to claim 1 or claim 2, wherein the compound represented by the general formula (1) is N-arylimine diacetic acid. The thermosetting resin composition according to item 1 or 2 of the scope of the patent application, wherein the thermosetting resin is selected from the group consisting of a polyimide precursor resin, a polyimide precursor resin, and a polymer. At least one of 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 item 1 or item 2 of the scope of patent application, which further includes a compound having an ethylenically unsaturated bond as a polymerizable compound. The thermosetting resin composition according to item 8 of the scope of patent application, further comprising a photopolymerization initiator. A cured film obtained by curing the thermosetting resin composition according to any one of claims 1 to 10 in the scope of patent application. The cured film according to item 11 of the scope of patent application, which is an interlayer insulating film for redistribution. A method for manufacturing a cured film, comprising: a step of applying the thermosetting resin composition according to any one of claims 1 to 10 to a substrate on a substrate; The step of curing the thermosetting resin composition is described. A semiconductor device includes a cured film as described in claim 11 or a cured film produced by the method for manufacturing a cured film as described in claim 13.