WO2015199220A1

WO2015199220A1 - Thermosetting resin composition, cured film, manufacturing method for cured film, and semiconductor device

Info

Publication number: WO2015199220A1
Application number: PCT/JP2015/068508
Authority: WO
Inventors: 一郎小山
Original assignee: 富士フイルム株式会社
Priority date: 2014-06-27
Filing date: 2015-06-26
Publication date: 2015-12-30
Also published as: TWI644979B; TW201600564A; JPWO2015199220A1

Abstract

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

Description

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

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

Thermosetting resins that are cured by cyclization, such as polyimide resins, polyamideimide resins, and polybenzoxazole resins, are excellent in heat resistance and insulation, and are therefore used in insulating layers of semiconductor devices.
Moreover, since the above thermosetting resin has low solubility in a solvent, it is used in the state of a precursor resin (polyimide precursor resin, polyamideimide precursor resin, polybenzoxazole precursor resin) before the cyclization reaction. And after applying to a board | substrate etc., it heats and cyclizes a thermosetting resin, and forms the cured film.

For example, Patent Documents 1 and 2 disclose a composition containing a polyimide precursor resin having a radical polymerizable group and a photopolymerization initiator.
Patent Document 3 discloses a composition containing an ester of polyamide in which an ester group contains a photopolymerizable olefin double bond.
Patent Document 4 discloses a composition containing 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 polyimide precursor containing a polyimide precursor, a thermal base generator composed of a neutral compound that undergoes thermal decomposition by heating at a temperature of 200 ° C. or less, and generates a secondary amine, and a solvent. A body resin composition is disclosed.

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

JP-A-63-27834 Japanese Patent Application Laid-Open No. 07-5688 U.S. Pat. No. 4,548,891 JP 2003-084435 A JP 2006-282880 A JP 2007-56196 A JP 2009-237175 A JP 2008-63553 A

Thermosetting resins that cyclize and cure with a base, such as polyimide precursor resins, polyamideimide precursor resins, and polybenzoxazole precursor resins, can form cured films with excellent heat resistance. A heat treatment at a high temperature has been required for the cyclization reaction of the thermosetting resin. For this reason, when an insulating layer of a semiconductor device is formed using such a thermosetting resin, there is a possibility that electronic parts and the like may be thermally damaged by heating during the cyclization reaction of the thermosetting resin. There is a need for further reduction of the cyclization temperature.

The inventors have examined the compositions disclosed in Patent Documents 1 to 4, and found that the temperature of the cyclization reaction of the thermosetting resin is high and the curability at low temperature is not sufficient.

In Patent Document 5, as described in paragraph 0014, a large solubility contrast can be obtained regardless of the type of polyimide precursor resin, and as a result, the shape is good while maintaining a sufficient process margin. The invention aims to provide a photosensitive resin composition capable of obtaining a pattern. In order to achieve this object, an N-aromatic glycine derivative is used as a photobase generator. That is, in Patent Document 5, an exposed portion is cured by imidizing a polyimide precursor resin using an amine generated by irradiating light to an N-aromatic glycine derivative as a catalyst, thereby exposing an exposed portion and an unexposed portion. A difference in solubility is given between the two.
However, Patent Document 5 does not discuss the reduction of the cyclization temperature, and in the examples, imidization is performed by heating at 300 ° C. for 1 hour.

Patent Document 6 uses a thermal base generator composed of a neutral compound that undergoes thermal decomposition by heating at a temperature of 200 ° C. or lower to generate a secondary amine. For example, it was found that this thermal base generator is in an equilibrium state of dissociation and non-dissociation in the composition. For this reason, it was found that the cyclization reaction of the polyimide precursor resin progresses during storage of the composition and gelation is likely to occur, and the stability is poor.

On the other hand, Patent Documents 7 and 8 disclose that a carboxylic acid compound such as N-phenyliminodiacetic acid is used in an image forming layer of a lithographic printing plate precursor or a laser-decomposable resin composition. There is no description or suggestion about lowering the cyclization temperature of the curable resin.

Therefore, an object of the present invention is to enable a cyclization reaction of a thermosetting resin at a low temperature, and to provide a thermosetting resin composition having excellent stability, a cured film using such a thermosetting resin composition, and curing. An object of the present invention is to provide a film manufacturing method and a semiconductor device.

As a result of detailed studies, the present inventor used a compound represented by the following general formula (1) in combination with a thermosetting resin that is cyclized and cured with a base, so that the cyclization temperature of the thermosetting resin is reduced. The present inventors have found that a thermosetting resin composition that is low and excellent in stability can be provided, and the present invention has been completed. 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 and cured by a base;

In general formula (1), A represents a p-valent organic group, L ¹ represents an (m + 1) -valent linking group, L ² represents an (n + 1) -valent linking group, and m represents an integer of 1 or more. 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 A is an aromatic ring group in the general formula (1).
<3> The thermosetting resin composition according to <1> or <2>, in which A is a benzene ring in the general formula (1).
<4> The thermosetting resin composition according to any one of <1> to <3>, wherein in 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-aryliminodiacetic acid.
<7> The thermosetting resin according to any one of <1> to <6>, wherein the thermosetting resin is at least one selected from a polyimide precursor resin, a polyamideimide precursor resin, and a polybenzoxazole precursor resin. Resin composition.
<8> The thermosetting resin composition according to any one of <1> to <7>, wherein the thermosetting resin has an ethylenically unsaturated bond.
<9> The thermosetting resin composition according to any one of <1> to <8>, further comprising a compound having an ethylenically unsaturated bond as the polymerizable compound.
<10> The thermosetting resin composition according to <8> or <9>, further containing a photopolymerization initiator.
<11> A cured film obtained by curing the thermosetting resin composition according to any one of <1> to <10>.
<12> The cured film according to <11>, which is an interlayer insulating film for rewiring.
<13> A cured film comprising a step of applying the thermosetting resin composition according to any one of <1> to <10> to a substrate, and a step of curing the thermosetting resin composition applied to the substrate. Manufacturing method.
<14> A semiconductor device having the cured film according to <11> or the cured film manufactured by the method according to <13>.
<15> A thermal base generator, which is a compound represented by the following general formula (1);

In general formula (1), A represents a p-valent organic group, L ¹ represents an (m + 1) -valent linking group, L ² represents an (n + 1) -valent linking group, and m represents an integer of 1 or more. N represents an integer of 1 or more, and p represents an integer of 1 or more.
<16> The thermal base generator according to <15>, wherein A is an aromatic ring group in the general formula (1).
<17> The thermal base generator according to <15> or <16>, wherein A in the general formula (1) is a benzene ring.
<18> The thermal base generator according to any one of <15> to <17>, wherein in formula (1), L ¹ and L ² are each independently an alkylene group.
<19> The thermal base generator according to any one of <15> to <18>, wherein in general formula (1), m, n, and p are each 1.
<20> The thermal base generator according to any one of <15> to <19>, wherein the compound represented by the general formula (1) is N-aryliminodiacetic acid.

INDUSTRIAL APPLICABILITY According to the present invention, a thermosetting resin cyclization reaction can be performed at a low temperature, and a thermosetting resin composition having excellent stability, a cured film using such a thermosetting resin composition, and a method for producing the cured film And it became possible to provide semiconductor devices.

It is the schematic which shows the structure of one Embodiment of the semiconductor device of this invention.

The description of the components in the present invention described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “active light” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, “exposure” in this specification is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays, EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) allyl” represents both “allyl” and “methacryl”, or “(Meth) acryl” represents either “acryl” and “methacryl” or any one, and “(meth) acryloyl” represents both “acryloyl” and “methacryloyl”, or Represents either.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, solid content concentration is the mass percentage of the mass of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
In this specification, a weight average molecular weight is defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. Unless otherwise stated, the eluent is measured using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution.

<Thermosetting resin composition>
The thermosetting resin composition of the present invention contains a compound represented by the general formula (1) and a thermosetting resin that is cyclized by a base to promote curing.
With the thermosetting resin composition of this invention, the cyclization reaction of a thermosetting resin can be performed at low temperature, and it can be set as the thermosetting resin composition excellent in stability. This effect is presumed to be due to the following reason. That is, the compound represented by the general formula (1) is acidic at room temperature, but has been neutralized and inactivated until the carboxyl group is decarboxylated or dehydrated and lost by heating. The site becomes active and basic. And it is thought that the cyclization reaction of a thermosetting resin was accelerated | stimulated with the base generate | occur | produced from the compound represented by General formula (1). Moreover, since the compound represented by General formula (1) is acidic at room temperature as above-mentioned, it does not promote the cyclization reaction of a thermosetting resin. For this reason, even if it preserve | saves for a long time in the state which mixed the compound represented by General formula (1), and the thermosetting resin which cyclizes with a base and hardening is accelerated | stimulated, reaction will advance if it does not heat. It is preferable.
The present invention will be described in detail below.

<< Compound Represented by Formula (1) >>
The thermosetting resin composition of the present invention contains a compound represented by the general formula (1). This compound generates a base when heated and functions as a thermal base generator. Before heating, it usually exists as an acidic compound. In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. Stir. The value of the solution measured at 20 ° C. using a pH meter is less than 7.

In general formula (1), A represents a p-valent organic group, L ¹ represents an (m + 1) -valent linking group, L ² represents an (n + 1) -valent linking group, and m represents an integer of 1 or more. N represents an integer of 1 or more, and p represents an integer of 1 or more.

In general formula (1), A represents a p-valent organic group. Examples of the organic group include an aliphatic group and an aromatic ring group, and an aromatic ring group is preferable. By using A as an aromatic ring group, a base having a high boiling point can be easily generated at a lower temperature. By increasing the boiling point of the generated base, it is difficult to volatilize or decompose by heating during curing of the thermosetting resin, and the cyclization of the thermosetting resin can proceed more effectively.
Examples of the monovalent aliphatic group include an alkyl group, a cycloalkyl group, and an alkenyl group.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear or 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 tert-butyl group, and a dodecyl group.
The cycloalkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 3 to 10 carbon atoms. The cycloalkyl group may have a substituent or may be unsubstituted. Specific examples of the alkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, and the like.
The alkenyl group has preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 10 carbon atoms. The alkenyl group may be linear or 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 groups obtained by removing one or more hydrogen atoms from the above 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. Unsubstituted is preferred. Specific examples of the aromatic ring group include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acenaphthalene ring, phenanthrene ring, anthracene ring, naphthacene 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, indolizine ring, indole ring, benzofuran Ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline ring, Antoren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring, and include phenazine ring, a benzene ring is most preferred.
In the aromatic ring group, a plurality of aromatic rings may be linked via a single bond or a linking group described later. As the linking group, for example, an alkylene group is preferable. The alkylene group is preferably linear or branched. Specific examples of the aromatic ring group in which a plurality of aromatic rings are linked through a single bond or a linking group include biphenyl, diphenylmethane, diphenylpropane, diphenylisopropane, triphenylmethane, and tetraphenylmethane.

Examples of the substituent that the organic group represented by A may have include, for example, 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 tert-butoxy group Aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group Group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group and other acyl groups; methylsulfanyl group and tert-butylsulfanyl group and other alkylsulfanyl groups; phenylsulfanyl group and p-tolylsulfanyl group and other aryls Fanyl group; alkyl group such as methyl group, ethyl group, tert-butyl group and dodecyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group and adamantyl group; phenyl group, p-tolyl group, xylyl group, Aryl groups such as cumenyl group, naphthyl group, anthryl group and phenanthryl group; hydroxy group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamido group; A monoalkylamino group; a dialkylamino group; an arylamino group; and a diarylamino group thioxy group; or a combination thereof.

L ¹ represents an (m + 1) -valent linking group, and L ² represents an (n + 1) -valent linking group. The linking group is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group (preferably a straight chain having 1 to 10 carbon atoms). A chain or a branched alkylene group), a cycloalkylene group (preferably a cycloalkylene group having 3 to 10 carbon atoms), an alkenylene group (preferably a straight chain or branched alkenylene group having 1 to 10 carbon atoms) or a combination of these linked Examples include groups. The total carbon number of the linking group is preferably 3 or less. The linking group is preferably an alkylene group, a cycloalkylene group or an alkenylene group, more preferably a linear or branched alkylene group, still more preferably a linear alkylene group, particularly preferably an ethylene group or a methyl group, and even more preferably a methylene group.

m and n 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 that the linking group represented by L ¹ and L ² can take. When m and n are 1, a tertiary amine having a high boiling point is likely to be generated by heating at 200 ° C. or lower. Furthermore, the stability of the 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 the organic group represented by A can take. When p is 1, a tertiary amine having a high boiling point is likely to be generated by heating at 200 ° C. or lower.

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

The compound represented by the general formula (1) is preferably a compound that generates a base when heated to 120 to 230 ° C., and more preferably a compound that generates a base at 120 to 200 ° C. The base generation temperature can be determined by, for example, using differential scanning calorimetry, heating the compound in a pressure-resistant capsule to 250 ° C. at 5 ° C./min, reading the peak temperature of the lowest exothermic peak, and taking this peak temperature as the base generation temperature. Can be measured.
The base generated by the compound represented by the general formula (1) is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a thermosetting resin can be lowered more.
The boiling point of the base generated by the compound represented by the general formula (1) is preferably 80 ° C. or higher, preferably 100 ° C. or higher, and more preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the 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. These can be used alone or in admixture of two or more. In the following formulae, Me represents a methyl group. Of the compounds shown below, (A-1) to (A-9), (A-13) to (A-17), (A-19), and (A-20) are preferred, and (A-1) , (A-2), (A-3), (A-4), (A-8), (A-9), and (A-19) are more preferable.

The content of the compound represented by the general formula (1) is preferably 0.1 to 50% by mass with respect to the total solid content of the thermosetting resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. When the content of the compound represented by the general formula (1) is in the above range, the thermosetting resin can be cyclized at a low temperature, and a cured film having excellent heat resistance is formed by a heat treatment at a low temperature. be able to.
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. It is preferable to contain.
1 type (s) or 2 or more types can be used for the compound represented by General formula (1). When using 2 or more types, it is preferable that a total amount is the said range.

<< Thermosetting resin >>
The thermosetting resin composition of the present invention contains a thermosetting resin that is cyclized by a base to accelerate curing. The thermosetting resin is preferably a heterocyclic-containing polymer precursor resin capable of forming a heterocyclic-containing polymer by causing a cyclization reaction by heating. The heterocyclic-containing polymer precursor resin is preferably at least one selected from a polyimide precursor resin, a polyamideimide precursor resin, and a polybenzoxazole precursor resin, and is a polyimide precursor resin or a polybenzoxazole precursor. A resin is more preferable, and a polyimide precursor resin is still more preferable. According to this aspect, it is easy to form a cured film having more excellent heat resistance. Further, these thermosetting resins have a high cyclization temperature, and conventionally cyclization was performed by heating to 300 ° C. or higher. However, according to the present invention, even these thermosetting resins are 300 The cyclization reaction can be sufficiently advanced by heating at a temperature of less than or equal to 200 ° C. (preferably less than or equal to 200 ° C., more preferably less than or equal to 180 ° C.), and the effects of the present invention can be obtained more remarkably.
In the present invention, the thermosetting resin preferably has an ethylenically unsaturated bond, and more preferably a polyimide precursor resin having an ethylenically unsaturated bond. When the thermosetting resin has an ethylenically unsaturated bond, it is easy to form a cured film having more excellent heat resistance. Furthermore, when performing pattern formation by photolithography, the sensitivity can be increased.
The content of the thermosetting resin in the thermosetting resin composition of the present invention is preferably 30 to 90% by mass with respect to the total solid content of the thermosetting resin composition. The lower limit is more preferably 40% by mass or more, and further preferably 50% by mass or more.

<<< Polyimide precursor resin, polyamideimide precursor resin >>>
The polyimide precursor resin is not particularly limited as long as it is a compound capable of being polyimidized, but is preferably a polyimide precursor resin having an ethylenically unsaturated bond.
The polyamideimide precursor resin is not particularly limited as long as it is a compound that can be polyamideimided, but is preferably a polyamideimide precursor resin having an ethylenically unsaturated bond.
The polyimide precursor resin and the polyamideimide precursor resin are most preferably a compound containing a repeating unit represented by the following general formula (2).

In 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, R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group.

A ¹ and A ² each independently represents an oxygen atom or —NH—, preferably an oxygen atom.

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a diamine residue remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, cycloaliphatic or aromatic diamines.
Specific examples include diamine residues remaining after removal of the amino groups of the following diamines.
1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1, 2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3 -Aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- and p-phenylenediamine, diaminotoluene, 4,4'- and 3,3'-diaminobiphenyl, 4,4'- and 3,3'-diaminodiphenyl ether, 4,4'- and 3,3'-diaminodiphenylmethane, 4, '-And 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4'- and 3,3'-diaminobenzophenone, 3,3'-dimethyl-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2 , 2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 4,4′-diaminoparaterphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bi [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) ) Anthracene, 3,3′-dimethyl-4,4′-diaminodiphenylsulfone, 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-bi [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) 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, bis [4- (4-aminophenoxy) phenyl ] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 3,3-dihydroxy-4,4′-diaminobiphenyl, 9,9′- Bis (4-aminophenyl) fluorene, 4,4′-dimethyl-3,3′-diaminodiphenylsulfone, 3,3 ′, 5 5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,4- 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) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, diaminoanthraquinone, 1,3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1,5-bis ( -Aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 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-trifluoromethylphenoxy) benzene, 4,4'-bis (4-amino-2) -Trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphe Nyl, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4′-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [ 4- (4-Amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4, Removal of amino group of at least one diamine selected from 4′-diaminobiphenyl, 2,2 ′, 5,5 ′, 6,6′-hexafluorotriden and 4,4 ′ ″-diaminoquaterphenyl A diamine residue remaining later.

R ¹¹² represents a tetravalent organic group. Examples of the tetravalent organic group include a tetracarboxylic acid residue remaining after removal of the anhydride group from tetracarboxylic dianhydride.
Specific examples include tetracarboxylic acid residues remaining after the removal of anhydride groups from the following tetracarboxylic dianhydrides.
Pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′ , 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethane tetracarboxylic dianhydride 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic Acid dianhydride, dianhydride of oxydiphthalic acid, 3,3 ′, 4,4′-diphenyloxide tetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3, 6,7-Naphthalene tetracarboxylic acid Anhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxy) Phenyl) 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-perylenetetracarboxylic 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) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride And a tetracarboxylic acid residue remaining after removal of the anhydride group from at least one tetracarboxylic dianhydride selected from these C1-C6 alkyls and C1-C6 alkoxy derivatives.

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 developer is preferably used.

From the viewpoint of solubility in an 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 group 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 specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably a HO group.
When R ¹¹³ and R ¹¹⁴ are a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl, the solubility in an aqueous developer is good, and it is particularly suitable as a negative thermosetting resin composition. Can be used.

From the viewpoint of solubility in organic solvents, R ¹¹³ and R ¹¹⁴ are preferably monovalent organic groups. The monovalent organic group is particularly preferably an alkyl group, a cycloalkyl group, or an aromatic ring group.
Specifically, the alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Group, dodecyl group, tetradecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group.
Specifically, the cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Can be mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity.
Specific examples of the aromatic ring group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, Anthracene ring, naphthacene 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, indolizine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring Phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. A benzene ring is most preferred.

In the general formula (2), it is preferable that at least one of R ¹¹³ and R ¹¹⁴ represents a polymerizable group. According to this, sensitivity and resolution can be improved.

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 amino group. Of these, a group having an ethylenically unsaturated bond is preferred because of its good sensitivity. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.

In the formula (III), R ²⁰⁰ represents hydrogen or methyl, and methyl is more preferable.
In the formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, —CH ₂ CH (OH) CH ₂ — or a polyoxyalkylene group having 4 to 30 carbon atoms.
Examples of suitable R ²⁰¹ are ethylene, propylene, trimethylene, tetramethylene, 1,2-butanediyl, 1,3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, —CH ₂ CH (OH) CH ₂ —, And ethylene, propylene, trimethylene, and —CH ₂ CH (OH) CH ₂ — are more preferable.
Particularly preferably, R ²⁰⁰ is methyl and R ²⁰¹ is ethylene.

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

The polyimide precursor resin and the polyamideimide precursor resin are repeating based on two or more different kinds of these groups in addition to the repeating structural unit of the above general formula (2) based on one kind of R ¹¹¹ or R ^112. Units may be included. Further, the polyimide precursor resin and the polyamideimide precursor resin may contain repeating units that are structural isomers. As examples of how the structural isomer pair of the unit of the general formula (2) appears, an example of the unit of the formula (2) derived from pyromellitic acid in which R ¹¹² is represented by a pyromellitic acid residue is shown below. (A ¹ and A ² = —O—).
Further, the polyimide precursor resin and the polyamideimide precursor resin may contain other types of repeating structural units in addition to the repeating unit of the general formula (2).

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

<<< Polybenzoxazole precursor resin >>>
The polybenzoxazole precursor resin is not particularly limited as long as it is a compound that can be converted into polybenzoxazole, but is preferably a polybenzoxazole precursor resin having an ethylenically unsaturated bond. In particular, the compound represented by the following general formula (3) is most preferable.

In 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 represents a hydrogen atom or a monovalent organic group. Represents.

R ¹²¹ represents a divalent organic group. As the divalent organic group, an aromatic ring group is preferable. Examples of the aromatic ring group include the following.

In the formula, A is a divalent group selected from the group consisting of —CH ₂ —, —O—, —S—, —SO ₂ —, —CO—, —NHCO—, —C (CF ₃ ) ₂ —. Represents.

R ¹²² represents a tetravalent organic group. The tetravalent organic group is preferably a bisaminophenol residue 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 represented by 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′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2 -Bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) ) Hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydride) Xylphenyl) propane, 4,4′-diamino-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- Examples include dihydroxybenzene. These bisaminophenols may be used alone or in combination.

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

In the formula, X ₁ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—. In the above structure, —OH and —NH ₂ contained in the structure of the general formula (A) are bonded to each other at the ortho position (adjacent position).

R ¹²³ and R ^{124 each} represent a hydrogen atom or a monovalent organic group, and at least one of R ¹²³ and R ¹²⁴ preferably represents a polymerizable group. As a polymeric group, the aspect demonstrated by ^R113 and ^R114 of General formula (2) mentioned above is the same, and its preferable range is also the same.

The polybenzoxazole precursor resin may contain other types of repeating structural units in addition to the repeating unit of the general formula (3).

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, for example, by gel filtration chromatography calibrated with polystyrene.

<< polymerizable compound >>
The thermosetting resin composition of the present invention may contain a polymerizable compound other than the compound represented by the above general formula (1) and the thermosetting resin. By containing a polymerizable compound, a cured film having more excellent heat resistance can be formed. Furthermore, pattern formation by photolithography can also be performed.
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 is a group that can be polymerized by the action of actinic rays, radiation, or radicals, and examples thereof include a group having an ethylenically unsaturated bond. As the group having an ethylenically unsaturated bond, a styryl group, a vinyl group, a (meth) acryloyl group and a (meth) allyl group are preferable, and a (meth) acryloyl group is more preferable. That is, the polymerizable compound used in the present invention is preferably a compound having an ethylenically unsaturated bond, more preferably a (meth) acrylate compound, and still more preferably an acrylate compound.
Polymerizable compounds are widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be any of chemical forms such as monomers, prepolymers, oligomers or mixtures thereof and multimers thereof.

In the present invention, a monomer type 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 2000 or less, more preferably a low molecular compound having a molecular weight of 1500 or less, and a low molecular compound having a molecular weight of 900 or less. More preferably it is. The molecular weight of the polymerizable monomer is usually 100 or more.
The oligomer type polymerizable compound (hereinafter also referred to as polymerizable oligomer) is typically a polymer having a relatively low molecular weight, and is a polymer in which 10 to 100 polymerizable monomers are bonded. Is preferred. Regarding the molecular weight, the polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) method is preferably 2000 to 20000, more preferably 2000 to 15000, and most preferably 2000 to 10,000.

The number of functional groups of the polymerizable compound in the present invention means the number of polymerizable groups in one molecule.
From the viewpoint of resolution, the polymerizable compound preferably contains at least one bifunctional or higher functional polymerizable compound containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher functional polymerizable compound. Is more preferable.
Moreover, it is preferable that the polymeric compound in this invention contains at least 1 sort (s) of polymeric compounds more than trifunctional from the point that a three-dimensional crosslinked structure can be formed and heat resistance can be improved. Also, a mixture of a bifunctional or lower polymerizable compound and a trifunctional or higher functional polymerizable compound may be used.

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.), esters, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, amides of unsaturated carboxylic acids and polyvalent amine compounds, and multimers thereof. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid.

Specific examples of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol diacrylate. , Propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetra Ethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Pentaerythritol diacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, isocyanuric acid ethylene oxide modified triacrylate, polyester acrylate There are oligomers and the like.

Methacrylic acid esters 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-hydroxyp Epoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

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

Examples of other esters include aliphatic alcohol esters described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and JP-A-59-5240. Those having an aromatic skeleton described in JP-A-59-5241, JP-A-2-226149, and those containing an amino group described in JP-A-1-165613 are also preferably used.

Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylic. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.

Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

In addition, urethane-based addition-polymerizable monomers produced using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Etc.
CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (A)
(However, R ⁴ and R ⁵ represent H or CH _3. )
Further, urethane acrylates as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable.

As the polymerizable compound, the compounds described in paragraph No. 0095 to paragraph No. 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

Moreover, as a polymeric compound, the compound which has a boiling point of 100 degreeC or more under a normal pressure is also preferable. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (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 tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane (meth) acrylates as described in JP-B-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in JP-A-2008-292970, paragraph numbers 0254 to 0257 are also suitable. Moreover, the polyfunctional (meth) acrylate obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid etc. can be mentioned.
Other preferred polymerizable compounds include groups having a fluorene ring and an ethylenically unsaturated bond described in JP 2010-160418 A, JP 2010-129825 A, Japanese Patent No. 4364216, and the like. It is also possible to use a compound having two or more and a cardo resin.
Further, other examples of the polymerizable compound include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. Examples thereof include vinylphosphonic acid compounds described in the publication. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

In addition to the above, polymerizable compounds represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the general formula, n is an integer of 0 to 14, and m is an integer of 1 to 8. A plurality of R and T present in one molecule may be the same or different.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of the plurality of Rs is —OC (═O) CH═CH ₂ , or — represents a OC (= O) C (CH 3) = groups represented by CH _2.
As specific examples of the polymerizable compounds represented by the above general formulas (MO-1) to (MO-5), the compounds described in paragraphs 0248 to 0251 of JP-A-2007-26979 are disclosed in the present invention. Can also be suitably used.

Further, compounds described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a polymerizable compound.

As a polymerizable compound, dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.) ) Dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylates (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol 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 phosphoric acid group. The polyfunctional monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. More preferred is a polyfunctional monomer having a carboxylic acid, and particularly preferred in this ester is that the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polyfunctional monomer having an acid group, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polyfunctional monomer is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Further, the curability 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. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Among these, a polymerizable compound having a caprolactone structure represented by the following general formula (B) is preferable.

General formula (B)

(In the formula, all six Rs are groups represented by the following general formula (C), or 1 to 5 of the six Rs are groups represented by the following general formula (C). And the remainder is a group represented by the following general formula (D).)

General formula (C)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.)

Formula (D)

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

Such a polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (m = 1 in the above general formulas (B) to (D), Number of groups represented by formula (C) = 2, a compound in which R ¹ is all hydrogen atoms), DPCA-30 (formula, m = 1, number of groups represented by formula (C) = 3 , Compounds in which R ¹ is all hydrogen atoms), DPCA-60 (same formula, m = 1, number of groups represented by formula (C) = 6, compounds in which R ¹ is all hydrogen atoms), DPCA -120 (a compound in which m = 2 in the formula, the number of groups represented by the general formula (C) = 6, and all R ¹ are hydrogen atoms).
In this invention, the polymeric compound which has a caprolactone structure can be used individually or in mixture of 2 or more types.

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

In general formulas (i) and (ii), each E independently represents — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — Each y independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (i), the total number of (meth) acryloyl groups is 3 or 4, each m 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) acryloyl groups is 5 or 6, each n 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 general formula (i), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
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 general formula (ii), n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
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.
In general formula (i) or general formula (ii), — ((CH ₂ ) _y CH ₂ O) — or — ((CH ₂ ) _y CH (CH ₃ ) O) — The form which couple | bonds with is preferable. In particular, in the general formula (ii), a form in which all six Xs are acryloyl groups is preferable.

The compound represented by the general formula (i) or (ii) has a ring-opening skeleton by a ring-opening addition reaction of pentaerythritol or dipentaerythritol with ethylene oxide or propylene oxide, which is a conventionally known process. It can be synthesized from the step of bonding and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. 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 (ii).

Among the compounds represented by the general formulas (i) and (ii), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.

Examples of commercially available polymerizable compounds represented by general formulas (i) and (ii) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.

Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, and the like. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are described as polymerizable compounds. Monomers can also be used.
Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA- 7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoei Co., Ltd.), Blemmer PME400 (Manufactured by NOF Corporation)).

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

* In the formula is a connecting hand.

Specific examples of the polymerizable compound having the partial structure include, for example, trimethylolpropane tri (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, pentaerythritol tris. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, etc. In the present invention, these polymerizable compounds can be particularly preferably used.

In the thermosetting resin composition of the present invention, the content of the polymerizable compound is 1 to 50% by mass with respect to the total solid content of the thermosetting resin composition from the viewpoint of good curability and heat resistance. preferable. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. As the polymerizable compound, one kind may be used alone, or two or more kinds may be mixed and used.
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 90/10. Most preferred is ˜50 / 50. If the mass ratio of a thermosetting resin and a polymeric compound is the said range, the cured film excellent in sclerosis | hardenability and heat resistance can be formed.

<< Thermal polymerization initiator >>
The thermosetting resin composition of the present invention may contain a thermal polymerization initiator. A known thermal polymerization initiator can be used as the thermal polymerization initiator.
The thermal polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the polymerizable compound. By adding the thermal polymerization initiator, the polymerization reaction of the polymerizable compound can be advanced when the cyclization reaction of the thermosetting resin is advanced. In addition, when the thermosetting resin contains an ethylenically unsaturated bond, since the polymerization reaction of the thermosetting resin can be allowed to proceed together with the cyclization of the thermosetting resin, higher heat resistance can be achieved. .
Thermal polymerization initiators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens. Examples thereof include a compound having a bond and an azo compound. Among these, organic peroxides or azo compounds are more preferable, and peroxides are particularly preferable.
Specifically, compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554 can be mentioned.
In a commercial item, perbutyl Z (made by NOF Corporation) can be used conveniently.

When the thermosetting resin composition of the present invention has a thermopolymerization initiator, the content of the thermopolymerization initiator is preferably 0.1 to 50% by mass with respect to the total solid content of the thermosetting resin composition. More preferably, the content is 1 to 30% by mass, and particularly preferably 0.1 to 20% by mass. Further, the thermal polymerization initiator is preferably contained in an amount of 0.1 to 50 parts by weight, and more preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the polymerizable compound. According to this aspect, it is easy to form a cured film having more excellent heat resistance.
Only one type of thermal polymerization initiator may be used, or two or more types may be used. When there are two or more thermal polymerization initiators, the total is preferably in the above range.

<< Sensitizing dye >>
The thermosetting resin composition of the present invention may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state is brought into contact with the compound represented by the general formula (1), a thermal polymerization initiator, a photopolymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur. Thus, the compound represented by the general formula (1), the thermal polymerization initiator, and the photopolymerization initiator are decomposed by causing a chemical change to generate radicals, acids, or bases.

Examples of preferable sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the range of 300 nm to 450 nm. For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9.10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones , Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin, acrylic) Flavins), anthraquinones (eg, anthraquinones), squariums (eg, squalium), coumarins (eg, 7-diethylamino-4-methylcoumarin), phenothia Emissions such, styryl benzenes, distyryl benzenes, and the like carbazoles like.

Among them, in the present invention, it is preferable to combine with polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene), thioxanthones, distyrylbenzenes, and styrylbenzenes from the viewpoint of starting efficiency, and have an anthracene skeleton. More preferably, the compound is used. Particularly preferred specific compounds include 9,10-diethoxyanthracene and 9,10-dibutoxyanthracene.

When the thermosetting resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass based on the total solid content of the thermosetting resin composition. 1 to 15% by mass is more preferable, and 0.5 to 10% by mass is even more preferable. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

<< photopolymerization initiator >>
The thermosetting resin composition of the present invention may contain a photopolymerization initiator. When the thermosetting resin composition of the present invention contains a photopolymerization initiator, the thermosetting resin composition is applied to a semiconductor wafer or the like to form a layered composition layer, and then irradiated with light. Curing by radicals or acids occurs, and the solubility in the light irradiation part can be reduced. For this reason, there exists an advantage that the area | region from which solubility differs according to the pattern of an electrode can be simply created by exposing the said composition layer through the photomask with the pattern which masked only the electrode part, for example.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate a polymerization reaction (crosslinking reaction) of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

As the photopolymerization initiator, known compounds can be used without limitation. For example, halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, those having a trihalomethyl group), Acylphosphine compounds such as acylphosphine oxide, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo series Examples thereof include compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, and the like.

Examples of halogenated hydrocarbon compounds having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compound described in JP-A-62-258241, compound described in JP-A-5-281728, compound described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

Examples of the compounds described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloro Methyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 (2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl)- 1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) 1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3 , 4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4-oxa And diazole).

Further, as photopolymerization initiators other than those mentioned above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, etc. Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (eg, 3- (2-benzofuranoyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1 -Pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (5,7-di-n-propoxycoumarin), 3,3'-ca Bonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP No. 2002-363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphos Zinc oxide, bis (2,6-dimethoxybenzoyl) -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-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

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, benzophenone tetracarboxylic acid or its tetramethyl ester, 4,4'-bis (dialkylamino) benzophenones (eg, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bisdicyclohexylamino ) Benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1 -Propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether) Ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.
Kayacure DETX (manufactured by Nippon Kayaku) is also suitably used as a commercial product.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 whose absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used.
As the acylphosphine initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Preferred oxime compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

Examples of oxime compounds include J.M. C. S. Perkin II (1979) p. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995), pp. 156-162. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A Nos. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
As commercially available products, IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) are also preferably used.

Further, compounds described in JP-A-2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, and a nitro group is introduced into the dye moiety. Compounds described in JP 2010-15025 A and U.S. Patent Publication No. 2009-292039, ketoxime compounds described in International Publication No. 2009-131189, U.S. Pat. No. 7,556,910 containing a triazine skeleton and an oxime skeleton in the same molecule. And compounds described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-ray light source may be used.
Moreover, the cyclic oxime compounds described in JP-A-2007-231000 and JP-A-2007-322744 can also be suitably used. Among cyclic oxime compounds, in particular, cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A have high light absorptivity and high sensitivity. preferable.
In addition, a compound described in JP-A-2009-242469, which is a compound having an unsaturated bond at a specific site of the oxime compound, can also be suitably used.
The most preferred oxime compound includes an oxime compound having a specific substituent described in JP-A-2007-2699779, an oxime compound having a thioaryl group disclosed in JP-A-2009-191061, and the like.

Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Compounds are preferred.
More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, trihalomethyltriazine compounds, α-aminoketones Most preferred is at least one compound selected from the group consisting of compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds, and most preferred are oxime compounds.

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 compound include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of high sensitivity. These acid generators can be used singly or in combination of two or more.
Specific examples include acid generators described in paragraphs [0073] to [0095] of JP2012-8223A.

When the thermosetting resin composition contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably based on the total solid content of the thermosetting resin composition. It is 0.1 to 20% by mass, and more preferably 0.1 to 10% by mass. In addition, the photopolymerization initiator is preferably contained in an amount of 1 to 20 parts by mass, more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound.
Only one type of photopolymerization initiator may be used, or two or more types may be used. When there are two or more photopolymerization initiators, the total is preferably in the above range.

<< Chain transfer agent >>
The thermosetting resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can donate hydrogen to low-activity radical species to generate radicals, or can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.

When the thermosetting resin composition has a chain transfer agent, the preferable content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the thermosetting resin composition, The amount is preferably 1 to 10 parts by mass, particularly preferably 1 to 5 parts by mass.
Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably within the above range.

<< Polymerization inhibitor >>
A small amount of a polymerization inhibitor is preferably added to the thermosetting resin composition of the present invention in order to prevent unnecessary thermal polymerization of the thermoplastic resin and the polymerizable compound during production or storage.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and N-nitroso-N-phenylhydroxylamine aluminum salt.
When the thermosetting resin composition has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the thermosetting resin composition.
Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more polymerization inhibitors, the total is preferably in the above range.

<< Higher fatty acid derivatives, etc. >>
In order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the thermosetting resin composition of the present invention, and thermosetting in the drying process after coating. It may be unevenly distributed on the surface of the resin composition.
When the thermosetting resin composition has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the thermosetting resin composition.
Only one type of higher fatty acid derivative or the like may be used. When two or more types of higher fatty acid derivatives are used, the total is preferably within the above range.

<< Solvent >>
When the thermosetting resin composition of the present invention is layered by coating, it is preferable to mix a solvent. Any known solvent can be used without limitation as long as the thermosetting resin composition can be formed into a layer.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone δ-valerolactone, alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)) , 3-oxypropionic acid alkyl esters (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-D Ethyl 2-oxypropionate, etc.) (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, Ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and 2-oxy-2-methylpropionic acid Ethyl (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Methyl oxobutanoate, 2-oxobutane Ethyl acid and the like, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl 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, etc., and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptano , N- methyl-2-pyrrolidone, and the like, as well as aromatic hydrocarbons, e.g., toluene, xylene, anisole, limonene, dimethyl sulfoxide preferably as sulfoxides.

The solvent is preferably in the form of a mixture of two or more types from the viewpoint of improving the coated surface. In this case, particularly preferably, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexane It is a mixed solution composed of two or more selected from pentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

When the thermosetting resin composition has a solvent, the content of the solvent is preferably such that the total solid content concentration of the thermosetting resin composition is 5 to 80% by mass from the viewpoint of applicability, It is more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass.
One type of solvent may be sufficient and two or more types may be sufficient. When there are two or more solvents, the total is preferably in the above range.

<< Surfactant >>
Various surfactants may be added to the thermosetting resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
In particular, by containing a fluorosurfactant, liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, so that the uniformity of coating thickness and liquid-saving properties can be further improved. it can.
In the case of forming a film using a coating liquid containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coated surface The applicability to is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.

The fluorine content of the fluorosurfactant 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 within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility.
Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320 PF6520, PF7002 (manufactured by OMNOVA), and the like.

Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, manufactured by BASF) 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Rusupasu 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and W001 (manufactured by Yusho Co., Ltd.).

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

Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.

When the thermosetting resin composition has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably based on the total solid content of the thermosetting resin composition. Is 0.005 to 1.0 mass%.
Only one type of surfactant may be used, or two or more types may be used. When two or more surfactants are used, the total is preferably in the above range.

<< Other additives >>
The thermosetting resin composition in the present invention is within a range not impairing the effects of the present invention, and various additives, for example, a curing agent, a curing catalyst, a silane coupling agent, a filler, an adhesion promoter, Corrosion inhibitors such as antioxidants, ultraviolet absorbers, and aggregation inhibitors can be blended. When mix | blending these additives, it is preferable that the total compounding quantity shall be 3 mass% or less of solid content of a thermosetting resin composition.

<Preparation of thermosetting resin composition>
The thermosetting resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.

<Use 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 device, 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 device.
It can also be used as a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist).
Also. It can also be used for the production of printing plates such as offset printing plates or screen printing plates, for use in the etching of molded parts, for the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.

<Method for forming cured film>
Next, the formation method of the cured film of this invention is demonstrated.
The formation method of the cured film of this invention has the process of applying the thermosetting resin composition of this invention to a board | substrate, and the process of hardening the thermosetting resin composition applied to the board | substrate.

<< Step of applying thermosetting resin composition to substrate >>
Examples of the method of applying the thermosetting resin composition to the substrate include spinning, dipping, doctor blade coating, suspended casting, coating, spraying, electrostatic spraying, reverse roll coating, and the like. And reverse roll coating is preferred because it can be applied uniformly on the substrate. It is also possible to introduce the photosensitive layer onto a temporary, flexible carrier and then apply the final substrate, for example a copper-clad printed circuit board by layer transfer by lamination.

Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound And the like. These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.

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

It is preferable to dry after applying the thermosetting resin composition to the substrate. The drying is preferably performed at 60 to 150 ° C. for 10 seconds to 2 minutes, for example.
<< Step of heating >>
By heating the thermosetting resin composition applied to the substrate, the cyclization reaction of the thermosetting resin proceeds and a cured film having excellent heat resistance can be formed.
The heating temperature is preferably 50 to 300 ° C, more preferably 100 to 200 ° C, and particularly preferably 100 to 180 ° C.
According to the present invention, the amine species generated from the compound represented by the general formula (1) can act as a catalyst for the cyclization reaction of the thermosetting resin and promote the cyclization reaction of the thermosetting resin. The cyclization reaction of the curable resin can also be performed at a lower temperature. For this reason, a cured film having excellent 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 to the substrate and the step of heating. The pattern forming step can be performed by, for example, a photolithography method. For example, the method of performing through the process of exposing and the process of developing is mentioned. A case where a pattern is formed by photolithography will be described.

<< Exposure Step >>
In the exposure step, the thermosetting resin composition applied to the substrate is irradiated with a predetermined pattern of actinic rays or radiation.
The wavelength of the actinic ray or radiation varies depending on the composition of the thermosetting resin composition, but is preferably 200 to 600 nm, and more preferably 300 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, an LED light source, an excimer laser generator, etc. can be used, and i-line (365 nm), h-line (405 nm), g-line (436 nm), etc. Actinic rays having a wavelength of 300 nm to 450 nm can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
As is well known, photopolymerization of (meth) acrylate and similar olefin unsaturated compounds is prevented by oxygen in the air, particularly in a thin layer. This effect can be mitigated by known conventional methods such as temporary introduction of a coating layer of polyvinyl alcohol, pre-exposure or pre-conditioning in an inert gas.

<< Process for performing development process >>
In the step of developing, an unexposed portion of the thermosetting resin composition is developed using a developer. As the developer, an aqueous alkaline developer, an organic solvent, or the like can be used.
Examples of the alkali compound used in the aqueous alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicic acid. Examples include potassium, ammonia, and amine. Examples of amines include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, tetramethylammonium hydroxide. (TMAH) or tetraethylammonium hydroxide. Of these, alkali compounds containing no metal are preferred. Suitable aqueous alkaline developers are generally up to 0.5 N with respect to alkali, but may be diluted appropriately prior to use. For example, an aqueous alkaline developer having a concentration of about 0.15 to 0.4 N, preferably 0.20 to 0.35 N is also suitable. Only one type of alkali compound may be used, or two or more types may be used. When there are two or more types of alkali compounds, the total is preferably in the above range.
As an organic solvent, the thing similar to the solvent which can be used for the thermosetting resin composition mentioned above can be used.

In fields where the method for forming a cured film of the present invention can be applied, it can be preferably used for insulating films of semiconductor devices, interlayer insulating films for rewiring, and the like. In particular, since the resolution is good, it can be preferably used for an interlayer insulating film for rewiring in a three-dimensional mounting device.
It can also be used as a photoresist for electronics (galvanic resist, galvanic resist, etching resist, solder top resist).
Also. It can also be used for the production of printing plates such as offset printing plates or screen printing plates, for use in the etching of molded parts, for the production of protective lacquers and dielectric layers in electronics, in particular microelectronics.

<Semiconductor devices>
Next, an embodiment of a semiconductor device using the thermosetting resin composition of the present invention as an interlayer insulating film for rewiring will be described.
A semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
In this embodiment, the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described. However, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.

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

The stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and semiconductor elements 101b to 101d having through electrodes 102b to 102d are flip-chip connected.
That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the penetrating electrode 102c adjacent thereto by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. ing.

An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.

The stacked body 101 is stacked on the wiring board 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 board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).

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

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “%” and “parts” are based on mass.

(Synthesis Example of Compound Represented by General Formula (1)) [A-1 to A-10]
5 ml of water was placed in a 50 ml eggplant 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 10 mmol of allylamine was added dropwise and 4.6 mmol of potassium iodide was added. The temperature was raised to 90 ° C. and stirred for 5 hours. After cooling to room temperature, the precipitated solid was filtered. The obtained solid was reslurried in 2 ml of water and air-dried to obtain the desired product.

(Synthesis Example of Comparative Compound) [X-7, X-8]
5 ml of water, 10 mmol of aniline and 10 mmol of glutaconic acid or maleic acid were placed in a 50 ml eggplant flask and stirred for 5 minutes. 23 mmol of sodium hydroxide was added and heating was continued at 100 ° C. for 24 hours. After cooling to room temperature, the precipitated solid was filtered. The obtained solid was reslurried in 2 ml of water and air-dried to obtain the desired product.

Synthesis Example 1 [Polyimide precursor resin from pyromellitic dianhydride, 4,4′-oxydianiline and 3-hydroxybenzyl alcohol (B-1; polyimide precursor resin having no ethylenically unsaturated bond) )
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 added to 50 ml of N-methylpyrrolidone. Suspended and dried with molecular sieves. The suspension was heated at 100 ° C. for 3 hours. A few minutes after heating, a clear solution was obtained. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 ml N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. The viscosity increased during the addition of SOCl ₂ . After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. under reduced pressure for 3 days.

(Synthesis Example 2) [Synthesis of polyimide precursor resin (B-2; polyimide precursor resin having no ethylenically unsaturated bond) from pyromellitic dianhydride, 4,4′-oxydianiline and benzyl alcohol ]
14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours) and 14.22 g (131.58 mmol) benzyl alcohol were suspended in 50 ml N-methylpyrrolidone, Dried with molecular sieves. The suspension was heated at 100 ° C. for 3 hours. A few minutes after heating, a clear solution was obtained. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) pyridine and 90 ml N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl ₂ was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. The viscosity increased during the addition of SOCl ₂ . After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.08 g (58.7 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a speed of 5000 rpm for 15 minutes. The polyimide precursor resin was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ° C. under reduced pressure for 3 days.

Synthesis Example 3 [Polyimide precursor resin from pyromellitic dianhydride, 4,4′-oxydianiline and 2-hydroxyethyl methacrylate (B-3; polyimide precursor resin having an ethylenically unsaturated bond) Synthesis]
14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 7 g of pyridine and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to prepare a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester is chlorinated with SOCl ₂ , converted into a polyimide precursor resin with 4,4′-oxydianiline in the same manner as in Synthesis Example 1, and polyimide precursor in the same manner as in Synthesis Example 1. A body resin was obtained.

(Synthesis Example 4) [Pyromellitic dianhydride, 4,4′-oxydianiline, polyimide precursor resin from 3-hydroxybenzyl alcohol and 2-hydroxyethyl methacrylate (B-4; having ethylenically unsaturated bond) Synthesis of polyimide precursor resin)
14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 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.
Also, 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 mixed with 50 ml of N-methyl. After suspending in pyrrolidone and drying with molecular sieves, the suspension was heated at 100 ° C. for 3 hours to produce pyromellitic acid and 3-hydroxybenzyl alcohol diester.
After equimolar mixture of pyromellitic acid and 2-hydroxyethyl methacrylate diester and pyromellitic acid and 3-hydroxybenzyl alcohol diester was chlorinated with SOCl ₂ , 4,4′-oxy was synthesized in the same manner as in Synthesis Example 1. It converted into polyimide precursor resin with dianiline, and polyimide precursor resin was obtained by the same method as Synthesis Example 1.

Synthesis Example 5 [Polymer precursor resin from pyromellitic dianhydride, 4,4′-oxydianiline, benzyl alcohol and 2-hydroxyethyl methacrylate (B-5; polyimide precursor having an ethylenically unsaturated bond) Resin)
14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 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.
Also, 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. After drying with molecular sieves, the suspension was heated at 100 ° C. for 3 hours to produce pyromellitic acid and benzyl alcohol diester.
After equimolar mixture of pyromellitic acid and 2-hydroxyethyl methacrylate diester and pyromellitic acid and benzyl alcohol diester was chlorinated with SOCl ₂ , 4,4′-oxydianiline was prepared in the same manner as in Synthesis Example 1. It converted into the polyimide precursor resin and obtained the polyimide precursor resin by the method similar to the synthesis example 1.

<Base generation temperature>
Using differential scanning calorimetry (Q2000 manufactured by TA) (A) Heating a specific compound to 250 ° C at 5 ° C / min in a pressure-resistant capsule, reading the peak temperature of the lowest exothermic peak, and generating this peak temperature as a base Measured as temperature.

<Test Example 1>
[Examples 1 to 20, Comparative Examples 1 to 9]
The components described below were mixed to prepare a coating solution for the thermosetting resin composition.
<Composition of thermosetting resin composition>
(A) Specific compound:% by mass described in Table 1
(B) Polyimide precursor resin:% by mass described in Table 1
(C) Polymerizable compound:% by mass described in Table 1
(D) Thermal polymerization initiator: mass% listed in Table 1
(Other ingredients)
γ-butyrolactone: 60% by mass

Each thermosetting resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm and then applied to a silicon wafer by spinning (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 to form a uniform resin layer having a thickness of 10 μm on the silicon wafer.

[Example 21]
<Composition of thermosetting resin composition>
(A) Specific compound:% by mass described in Table 1
(B) Polyimide precursor resin:% by mass described in Table 1
(C) Polymerizable compound:% by mass described in Table 1
(E) Photopolymerization initiator: mass% listed in Table 1
(Other ingredients)
γ-butyrolactone: 60% by mass

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

<Evaluation>
[Curing property]
The thermosetting resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm and then applied to a silicon wafer by spinning (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 to form a uniform film having a thickness of 10 μm on the silicon wafer.
The film was scraped from the silicon wafer and subjected to thermogravimetric analysis (TGA measurement) in a state maintained at 250 ° C. in nitrogen to evaluate the cyclization time. Since the polyimide precursor resin undergoes a mass reduction as the cyclization reaction proceeds, the time until the mass reduction no longer occurs was evaluated according to the following criteria. The shorter the time, the faster the cyclization rate and the better results.
A: Over 10 minutes and under 30 minutes B: Over 30 minutes over 60 minutes C: Over 60 minutes over 120 minutes D: Over 120 minutes Or it did not cyclize.

[Stability]
After preparing the thermosetting resin composition, the container containing 10 g of the thermosetting resin composition was sealed and allowed to stand in an environment of 25 ° C. and humidity 65%. Stability was evaluated by the time until the cyclization of the thermosetting resin composition progressed and a solid was precipitated. The longer the time, the higher the stability of the composition and the better results. Precipitation of the solid was filtered through a mesh having a pore diameter of 0.8 μm, and the presence or absence of a mesh-like foreign matter was visually observed.
A: Solid precipitation was not observed even after 30 days B: Solid was precipitated within 30 days after 20 days C: Solid was precipitated within 20 days after 10 days D: Over 5 days, solid precipitated within 10 days E: Solid precipitated within 5 days

[Heat-resistant]
The film was scraped from the silicon wafer and subjected to thermogravimetric analysis (TGA measurement) in a state maintained at 350 ° C. for 3 hours in nitrogen to evaluate the mass reduction rate. The heat resistance was evaluated according to the following criteria. The smaller the mass reduction rate after 3 hours, the higher the heat resistance, which is a preferable result. The evaluation results are preferably AC.
A: 1% by mass or less B: 1% by mass to 5% by mass or less C: 5% by mass to 10% by mass or less D: More than 10% by mass

From the above results, it can be seen that the thermosetting resin compositions of Examples 1 to 21 are excellent in curability and stability.
In contrast, the thermosetting resin compositions of Comparative Examples 1 to 9 were inferior to the thermosetting resin compositions of the examples in at least one of curability and stability.

Abbreviations described in Table 1 are as follows.
(A) Specific compound A-1 to A-12: The following structure (wherein Me represents a methyl group).

X-1 to X-8 (Comparative compounds): The following structures (wherein Me represents a methyl group).

(B) Polyimide precursor resins B-1 to B-5: Polyimide precursor resins B-1 to B-5 synthesized in Synthesis Examples 1 to 5

(C) Polymerizable Compound C-1: NK Ester M-40G (Shin Nakamura Chemical Co., Ltd. Monofunctional Methacrylate Following Structure)

C-2: NK ester 4G (Shin Nakamura Chemical Co., Ltd., bifunctional metallate, following structure)

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

(D) Thermal polymerization initiator D-1: Perbutyl Z (manufactured by NOF Corporation, tert-butyl peroxybenzoate, 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 to a resin substrate on which a copper thin layer was formed by spinning (3500 rpm, 30 seconds). . The thermosetting resin composition applied to the resin substrate was dried at 100 ° C. for 5 minutes.
Subsequently, it heated at 180 degreeC for 20 minutes. In this way, a rewiring interlayer insulating film was formed.
This interlayer insulating film for rewiring was excellent in insulation.
Moreover, when a semiconductor device was manufactured using this rewiring interlayer insulating film, it was confirmed that it operated without problems.
In addition, the same effect was acquired even if it changed the polyimide precursor resin into the polyamide-imide precursor resin and the polybenzoxazole precursor.

100: Semiconductor devices 101a to 101d: Semiconductor element 101: Stacked bodies 102b to 10d: Through electrodes 103a to 103e: Metal bump 105: Rewiring layers 110, 110a, 110b: Underfill layer 115: Insulating layer 120: Wiring substrate 120a: Surface electrode

Claims

A thermosetting resin composition comprising a compound represented by the following general formula (1) and a thermosetting resin that is cyclized and cured by a base;

In general formula (1), A represents a p-valent organic group, L 1 represents an (m + 1) -valent linking group, L 2 represents an (n + 1) -valent linking group, and m represents an integer of 1 or more. N represents an integer of 1 or more, and p represents an integer of 1 or more.
The thermosetting resin composition according to claim 1, wherein A in the general formula (1) is an aromatic ring group.
The thermosetting resin composition according to claim 1 or 2, wherein A in the general formula (1) is a benzene ring.
The thermosetting resin composition according to any one of claims 1 to 3, wherein in the general formula (1), L 1 and L 2 are each independently an alkylene group.
The thermosetting resin composition according to any one of claims 1 to 4, wherein m, n and p are each 1 in the general formula (1).
6. The thermosetting resin composition according to claim 1, wherein the compound represented by the general formula (1) is N-aryliminodiacetic acid.
The thermosetting resin composition according to any one of claims 1 to 6, wherein the thermosetting resin is at least one selected from a polyimide precursor resin, a polyamideimide precursor resin, and a polybenzoxazole precursor resin. object.
The thermosetting resin composition according to any one of claims 1 to 7, wherein the thermosetting resin has an ethylenically unsaturated bond.
The thermosetting resin composition according to any one of claims 1 to 8, further comprising a compound having an ethylenically unsaturated bond as the polymerizable compound.
Furthermore, the thermosetting resin composition of Claim 8 or 9 containing a photoinitiator.
A cured film obtained by curing the thermosetting resin composition according to any one of claims 1 to 10.
The cured film according to claim 11, which is an interlayer insulating film for rewiring.
A method for producing a cured film, comprising: a step of applying the thermosetting resin composition according to any one of claims 1 to 10 to a substrate; and a step of curing the thermosetting resin composition applied to the substrate. .
A semiconductor device having the cured film according to claim 11 or the cured film manufactured by the method according to claim 13.