JPWO2019189110A1 - Photosensitive resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device - Google Patents

Abstract

The precursor of the heterocyclic polymer contains a precursor of a heterocyclic polymer, a thermobase generator and a radically polymerizable compound, the precursor of the heterocyclic polymer has a radically polymerizable group, and the radically polymerizable compound is a polymerizable functional group. A photosensitive resin composition, a cured film, and a laminate containing at least one radically polymerizable compound selected from the group consisting of a compound having 4 or more and a compound having 3 polymerizable functional groups and having a molecular weight of 400 or less. Body, cured film manufacturing method, and semiconductor device.

Description

The present invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.

Heterocyclic-containing polymers such as polyimide and polybenzoxazole are used as insulating films for semiconductor devices because they have excellent heat resistance and insulating properties. Then, for the film formation or molding thereof, it is often used in the state of a composition in which a precursor before the cyclization reaction having high solvent solubility, for example, a polyimide precursor and a polybenzoxazole precursor, is dissolved in a solvent. To. After applying this resin composition to a substrate or the like, it can be heated to cyclize the precursor to form a cured film.

As a resin composition of a precursor of such a heterocyclic polymer, for example, Patent Document 1 discloses a thermosetting resin composition containing a specific thermobase generator and a precursor of a heterocyclic polymer. ing. It is described that the cyclization of the thermosetting resin can be carried out at a low temperature, thereby providing a thermosetting resin composition having excellent stability.

International Publication No. 2015/199219

The development of compositions containing precursors of heterocyclic-containing polymers as described above has led to improved performance and manufacturing suitability to meet their needs in many applications. However, there are many unknown parts in these resins and their precursors, and the required characteristics are also diverse, so there is room for research and development. For example, in the case of an insulating film for a semiconductor device, various chemical treatments such as etching of a metal are performed to form the device structure. Therefore, resistance to chemical treatment is required. Further, sufficient breaking elongation is also required in consideration of the durability and impact resistance of the device. Usually, if the chemical resistance is improved, the elongation at break tends to decrease, and it is not easy to achieve both.
Therefore, an object of the present invention is to provide a photosensitive resin composition capable of achieving both chemical resistance of a cured resin and excellent elongation at break. Another object of the present invention is to provide a cured film, a laminate, a method for producing a cured film, and a semiconductor device using the photosensitive resin composition.

Based on the above problems, as a result of diligent studies by the present inventor, a specific compound was selected as a radically polymerizable compound and combined with a precursor of a heterocyclic polymer having a radically polymerizable group introduced and a thermobase generator. It was found that the above-mentioned problems can be solved by using the above-mentioned problem. Specifically, the above problems were solved by the following means <1>, preferably by <2> to <27>.
<1> Contains a precursor of a heterocyclic polymer, a thermobase generator, and a radically polymerizable compound.
The precursor of the heterocyclic polymer has a radically polymerizable group and has a radical polymerizable group.
The radically polymerizable compound contains at least one radically polymerizable compound selected from the group consisting of a compound having four or more polymerizable functional groups and a compound having three polymerizable functional groups and having a molecular weight of 400 or less. , Photosensitive resin composition.
<2> The photosensitive resin composition according to <1>, wherein the polymerizable functional group is a group independently selected from a vinylphenyl group, a vinyl group, and a (meth) acryloyl group.
<3> The photosensitive resin composition according to <1> or <2>, wherein the thermal base generator has a cation represented by the formula (101) or the formula (102);
In formulas (101) and (102), R ^{1 to} R ⁶ independently represent a hydrogen atom or a hydrocarbon group, and R ⁹ represents a hydrocarbon group.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the precursor of the heterocyclic polymer contains a polyimide precursor or a polybenzoxazole precursor.
<5> The photosensitive resin composition according to any one of <1> to <3>, wherein the precursor of the heterocyclic polymer contains a polyimide precursor.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the precursor of the heterocyclic-containing polymer contains a structural unit represented by the following formula (1);
In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are. Each independently represents a hydrogen atom or a monovalent organic group.
<7> The photosensitive resin composition according to <6>, wherein at least one of ^{R 113} and R ^{114 contains a radically polymerizable group.}
<8> The photosensitive resin composition according to <6> or <7>, wherein the ^{R 115 contains an aromatic ring.}
<9> The above R ¹¹¹ is ^{represented by −Ar 0} −L ⁰ −Ar ⁰ −, each Ar ⁰ is a divalent group independently containing an aromatic ring, and L ⁰ is a single bond, substituted with a fluorine atom. It is a group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO _2- , -NHCO- and a combination of two or more of these groups. The photosensitive resin composition according to any one of <6> to <8>.
<10> The photosensitive resin composition according to any one of <6> to <9>, wherein ^{R 111 is a group represented by the following formula (51) or formula (61);}
In formula (51), R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or difluoro. Methyl or trifluoromethyl group;
In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups or trifluoromethyl groups, respectively.
<11> The photosensitive resin composition according to any one of <1> to <10>, which contains a photopolymerization initiator.
<12> The photosensitive resin composition according to any one of <1> to <11>, wherein the mass ratio of the thermobase generator to the radically polymerizable compound is 1.0 to 80.
<13> Any one of <1> to <12>, wherein the radical polymerizable compound is used in an amount of 2.5 parts by mass or more and 62.5 parts by mass or less with respect to 100 parts by mass of the precursor of the heterocyclic polymer. The photosensitive resin composition according to 1.
<14> The photosensitive resin composition according to any one of <1> to <13>, which further contains a solvent.
<15> The photosensitive resin composition according to any one of <1> to <14>, which is subjected to development with a developing solution containing 90% by mass or more of an organic solvent.
<16> The photosensitive resin composition according to any one of <1> to <15>, which is used for forming an interlayer insulating film for a rewiring layer.
<17> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <16>.
<18> A laminated body having two or more layers of the cured film according to <17>.
<19> The laminate according to <18>, which has a metal layer between the cured films.
<20> The laminate according to <18> or <19>, which has 3 to 7 layers of the cured film.
<21> The photosensitive resin composition layer forming step of applying the photosensitive resin composition according to any one of <1> to <16> to a substrate to form a photosensitive resin composition layer, and the above-mentioned photosensitive. A method for producing a cured film, which comprises an exposure step of exposing the sex resin composition layer.
<22> The method for producing a cured film according to <21>, further comprising a developing step of developing the photosensitive resin composition layer after the exposure step.
<23> The method for producing a cured film according to <22>, wherein the developing step performs development using a developing solution containing 90% by mass or more of an organic solvent.
<24> The method for producing a cured film according to <22> or <23>, which comprises a post-development heating step of heating the photosensitive resin composition layer at a temperature of 50 to 450 ° C. after the developing step.
<25> The method for producing a cured film according to <24>, wherein the heating temperature is 50 to 250 ° C.
<26> The method for producing a cured film according to any one of <21> to <25>, wherein the film thickness of the cured film is 1 to 30 μm.
<27> A semiconductor device having the cured film according to <17> or the laminate according to any one of <18> to <20>.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive resin composition capable of achieving both chemical resistance of a cured resin and high elongation at break. Further, it has become possible to provide a cured film, a laminate, a method for producing a cured film, and a semiconductor device using the above-mentioned photosensitive resin composition.

It is a schematic diagram which shows the structure of one Embodiment of a semiconductor device.

The description of the components in the present invention described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having 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 the present specification, the “active ray” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like. Further, in the present invention, light means active light rays or radiation. Unless otherwise specified, the term "exposure" as used herein refers to not only exposure with far ultraviolet rays such as mercury lamps and excimer lasers, X-rays, and EUV light, but also drawing with particle beams such as electron beams and ion beams. Is also included in the exposure.
In the present specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.
In the present specification, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or. Representing either, "(meth) acryloyl" represents both "acryloyl" and "methacrylic", or either.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the desired action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
As used herein, the solid content concentration is the mass percentage of the mass of other components excluding the solvent with respect to the total mass of the composition. The solid content concentration refers to the concentration at 25 ° C. unless otherwise specified.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values by gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using any one or more of Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, the eluate shall be measured using THF (tetrahydrofuran). Unless otherwise specified, a detector having a wavelength of 254 nm for UV rays (ultraviolet rays) is used for detection.

The photosensitive resin composition of the present invention contains a precursor of a heterocyclic polymer, a thermobase generator and a radically polymerizable compound, and the precursor of the heterocyclic polymer has a radically polymerizable group and is described above. The radically polymerizable compound comprises at least one radically polymerizable compound selected from the group consisting of a compound having four or more polymerizable functional groups and a compound having three polymerizable functional groups and having a molecular weight of 400 or less. It is characterized by.
For the photosensitive resin composition containing the precursor of the heterocyclic polymer and the thermobase generator, the chemical resistance could be improved by using the polyfunctional radical polymerizable compound. However, that alone tends to reduce the elongation at break. Therefore, in the present invention, it is expected that not only the polymerizable compound but also the polymer and the thermobase generator are involved in the cross-linking, and it is expected that the cross-linking will be appropriately cleaved with the cyclization. For that purpose, it is understood that a form in which the site contributing to the cyclization reaction has a radically polymerizable group is preferable, and it has been found that the above configuration is used. It should be noted that the description of the mechanism here includes estimation, and the present invention is not construed as being limited thereto.

<Specific radically polymerizable compound>
The radically polymerizable compound used in the present invention (in this specification, may be referred to as "specific radically polymerizable compound") has a compound having four or more polymerizable functional groups and three polymerizable functional groups. It is at least one radically polymerizable compound selected from the group consisting of compounds having a molecular weight of 400 or less. The polymerizable functional group may be a group selected from a vinylphenyl group, a vinyl group, and a (meth) acryloyl group (in the present specification, these polymerizable functional groups are referred to as "polymerizable functional groups Ps"). preferable.
When the number of polymerizable functional groups is 4 or more, the number of functional groups of the specific radically polymerizable compound is preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. The molecular weight of the radically polymerizable compound having four or more polymerizable functional groups is preferably 1000 or less, more preferably 800 or less, and further preferably 600 or less. It is practical that the lower limit value is 400 or more. Within the above range, the crosslink density of the film is optimized, and the elongation at break and the chemical resistance are improved.
In the specific radically polymerizable compound, it is preferable that the radically polymerizable groups are separated from each other by a linking group having a linear structure of two or more atoms.
When there are three polymerizable functional groups, the molecular weight of the specific radically polymerizable compound is further preferably 370 or less, more preferably 340 or less, and further preferably 300 or less. It is practical that the lower limit value is 150 or more. Within the above range, the crosslink density of the film is optimized, and the elongation at break and the chemical resistance are improved.

The trifunctional radically polymerizable compound is preferably a compound represented by the following formula (P-1).
In formula (P-1), Ps is a group independently selected from a vinylphenyl group, a vinyl group and a (meth) acryloyl group, and ^RB1 is a hydrogen atom or a substituent (excluding a polymerizable functional group). ), And ^LP is an independent single bond or linking group, respectively. L ^Q is a linking group.

In the formula, Ps is preferably a (meth) acryloyl group.
^RB1 is an alkyl group which may have any substituent (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), -NH-Ps, or -CH _2. ^{-OL P-} Ps is preferable. Optional substituents, a hydroxyl group, a carboxyl group or with these and linking groups L ^P include groups that Tsu combination.

If L ^P is a linking group, the linking group, an oxygen atom, according to the sulfur atom, an amino group (NH), carbonyl group, (oligo) alkyleneoxy group, alkylene group, (oligo) alkylene amino groups, and combinations thereof Linking groups are exemplified.
Examples of the (oligo) alkyleneoxy group are preferably (oligo) methyleneoxy group, (oligo) ethyleneoxy group, and (oligo) propyleneoxy group. The linking group may be substituted with a substituent such as a hydroxyl group. The (oligo) alkyleneoxy group means that it may be a single alkyleneoxyki group or an oligoalkyleneoxy group in which a plurality of these are repeated. The number of repetitions of the (oligo) alkyleneoxy group is preferably 1 to 8, more preferably 1 to 4, and even more preferably 1 to 2.
The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkylene group may be substituted with a substituent such as a hydroxyl group.
The (oligo) alkyleneamino group is preferably a (oligo) methyleneamino group, a (oligo) ethyleneamino group, or a (oligo) propyleneamino group. The (oligo) alkyleneamino group may be substituted with a substituent such as a hydroxyl group. The number of repetitions of the (oligo) alkyleneamino group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
L ^P is a divalent linking group formed, the number of atoms involved in coupling excluding hydrogen atoms, preferably 1 to 30, more preferably from 2 to 20, more preferably 3 to 16.
L ^Q is a linking group, particular examples being illustrated linking group L ^P. Of these, an alkylene group is preferable, the number of carbon atoms is 1 to 12, more preferably 1 to 6, and further preferably 1 to 3. In particular, a methylene group or an ethylene group is preferable, and a methylene group is more preferable.

The radically polymerizable compound having four or more functions is preferably a compound represented by the following formula (P-2).
In formula (P-2), Ps is a group independently selected from a vinylphenyl group, a vinyl group and a (meth) acryloyl group, and ^RB2 is a hydrogen atom or a substituent (excluding a polymerizable functional group). ), ^LP is independently a single bond or a linking group, pm is an integer of 1 to 6, and pn is 1 or 2.
^{Ps, R B2, L P,} L Q , respectively, have the same meanings as ^{Ps, R B1, L P,} L Q in Formula (P-1), and the preferred range is also the same.
When pn is 1, ^RB2 is a hydrogen atom or a substituent (excluding polymerizable functional groups). As the substituent, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms) is preferable.
When pn is 2, ^RB2 is a divalent linking group. As the divalent linking group, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), an oxygen atom, a carbonyl group, an amino group (NH), or a combination thereof. The group related to.

It is also preferable that the radically polymerizable compound having four or more functions is a compound represented by the following formula (P-3).
In formula (P-3), Ps is a group independently selected from a vinylphenyl group, a vinyl group and a (meth) acryloyl group, L ^q is an rm + 1 valent linking group, and rm is 0 to 12. Is an integer of.
In the formula, Ps is preferably a (meth) acryloyl group.
L ^q is an alkylene group (preferably 1 to 60 carbon atoms, more preferably 3 to 40 carbon atoms, still more preferably 4 to 24), an amino group (NH), a carbonyl group, an oxygen atom, and a (oligo) alkyleneoxy group (for example). , (Oligo) methyleneoxy group, (oligo) ethyleneoxy group, (oligo) propyleneoxy group, the preferred number of repetitions is preferably 1 to 24, more preferably 3 to 18, further preferably 4 to 14), ( Oligo) alkyleneamino (NH) group (for example, (oligo) methyleneamino group, (oligo) ethyleneamino group, (oligo) propyleneamino group, the number of repetitions is preferably 1 to 24, more preferably 3 to 18. 4 to 14 are more preferable), or a combination thereof is preferable.
Ps not only ends of the L ^q, may be substituted on the way. L ^q is preferably a relatively long chain group, and the number of atoms involved in the connection excluding hydrogen atoms is preferably 5 or more and 100 or less, more preferably 6 or more and 50 or less, and 7 It is more preferably 40 or less.
rm is an integer of 0-12, preferably 1-8, more preferably 1-6.

Radically polymerizable compound represented by any of formulas (P-1) ~ (P -3) is the linking group represented by L ^{P +} L ^Q or L ^q in the compounds are present in the length of the corresponding Is preferable. Expressing this length as the ratio of mass in one molecule, the ratio expressed by ^{the formula amount of L p} + L ^Q or L ^q / molecular weight of the radically polymerizable compound × 100 is 5% by mass or more and 80% by mass or less. It is preferably 10% by mass or more and 70% by mass or less, and further preferably 15% by mass or more and 50% by mass or less.

Examples of specific radically polymerizable compounds are given below, but the present invention is not construed as being limited thereto.
l to o are independently natural numbers 1 to 3.
B-8 is a single compound of the above-mentioned tetrafunctional compound or trifunctional compound, or a mixture of the above-mentioned compounds.
l to q are independent natural numbers 1-3.

The content of the specific radically polymerizable compound is preferably 2% by mass or more, more preferably 5% by mass or more, and further preferably 10% by mass or more in the solid content of the photosensitive resin composition. preferable. The upper limit is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less.
The ratio of the specific radically polymerizable compound to the precursor of the heterocyclic polymer is preferably 2.5 parts by mass or more, preferably 6.2 parts by mass or more, based on 100 parts by mass of the precursor of the heterocycle-containing polymer. It is more preferable that the amount is 12.5 parts by mass or more. The upper limit is preferably 62.5 parts by mass or less, more preferably 37.5 parts by mass or less, and further preferably 25 parts by mass or less.
One kind or a plurality of specific radically polymerizable compounds may be used. When a plurality of items are used, the total amount is within the above range.

Further, the present invention may or may not contain a polymerizable compound other than the specific radically polymerizable compound (hereinafter, also referred to as another polymerizable compound) and a precursor of a heterocyclic ring-containing polymer described later. May be good.
One embodiment of the present invention is an embodiment in which another polymerizable compound is contained in an amount of more than 10% by mass of the content of the specific radically polymerizable compound. In the present embodiment, the content of the other polymerizable compound is preferably more than 10% by mass and 30% by mass or less of the content of the specific radically polymerizable compound. As the other polymerizable compound, a compound having a polymerizable functional group Ps can be used. The number of polymerizable groups contained in other polymerizable compounds may be, for example, one or two. The molecular weight of the other polymerizable compounds is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the polymerizable compound is preferably 100 or more. In addition to the above, other polymerizable compounds include compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds. As specific examples of other polymerizable compounds, among the compounds described in paragraphs 0102 to 0126 of International Publication No. 2017/104672, those which do not correspond to the specific radically polymerizable compounds are exemplified, and the contents thereof are described in the present specification. Incorporated in.
One embodiment of the present invention is an embodiment that does not substantially contain other radically polymerizable compounds. Substantially free means that the content of the polymerizable compound other than the specific radically polymerizable compound is 10% by mass or less of the content of the specific radically polymerizable compound, and is 5% by mass or less. Is more preferable, and it is more preferably 3% by mass or less, and even more preferably 1% by mass or less.

<Precursor of heterocyclic polymer>
The precursor of the heterocyclic polymer used in the present invention has a radically polymerizable group. The radically polymerizable group may be bonded to the side chain of the precursor of the heterocyclic polymer, or may be bonded to the main chain. Preferably, it is attached to the side chain.
The precursor of the heterocyclic polymer preferably contains a polyimide precursor or a polybenzoxazole precursor. As the polymer precursor, a polyimide precursor is more preferable, and a polyimide precursor containing a structural unit represented by the following formula (1) is further preferable.

<< Polyimide precursor >>
The polyimide precursor used in the present invention has a radically polymerizable group. The radically polymerizable group is preferably contained in the side chain.
It is more preferable that the polyimide precursor contains a structural unit represented by the following formula (1). With such a configuration, a composition having more excellent film strength can be obtained.
In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are. Each independently represents a hydrogen atom or a monovalent organic group.

A ¹ and A ² are independently oxygen atoms or NH, and an oxygen atom is preferable.

R ¹¹¹ represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, an aromatic heterocyclic group, or a group consisting of a combination thereof, and the number of carbon atoms is 2 to 20. A linear aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. Is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.
R ¹¹¹ is preferably derived from diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, the diamine is composed of a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. It is preferably a diamine containing an aromatic group having 6 to 20 carbon atoms, and more preferably a diamine containing an aromatic group. Examples of aromatic groups include:

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, −O−, −C (= O) −, −S−, −S. (= O) _2- , -NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O- , -C (= O) -, - more preferably a group selected _from, -CH 2 - - S- and _{-SO 2, - O -, -} S -, - SO 2 -, - C ( More preferably, it is a divalent group selected from the group consisting of CF ₃ ) ₂ − and −C (CH ₃ ) _{2 −.}

Specific examples of the diamine include 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; meta and paraphenylenediamine, diaminotoluene, 4,4'-and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diaminodiphenylsulfone , 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 (4,4'-diamino-2,2'-dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-amino) Phenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxy) Phenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4,4'-diaminoparatelphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) ) Phenyl] sulfone, bis [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) Nzen, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl- 4,4'-Diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy)) Phenyl] Hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether , 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl- 3,3'-Diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2- (3', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- And 2,5-diaminocumen, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl-paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, 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, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-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, parabis (4-amino-2-trifluoromethi) Ruphenoxy) Benzene, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 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, 4,4'-diamino-2,2'-bis (trifluoro) Included are at least one diamine selected from methyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl.

Further, the diamines (DA-1) to (DA-18) shown below are also preferable.

Further, a diamine having at least two or more alkylene glycol units in the main chain is also mentioned as a preferable example. A diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable. Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark). ) EDR-148, Jeffamine® EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine, etc., but are limited to these. Not done.
Jeffamine® KH-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® EDR-148, The structure of Jeffamine® EDR-176 is shown below.

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

In the formula (1), R ¹¹¹ is ^{represented by −Ar 0} −L ⁰ −Ar ⁰ −, each Ar ⁰ is a divalent group independently containing an aromatic ring, and L ⁰ is a single bond and a fluorine atom. It consists of an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted, -O-, -CO-, -S-, -SO _2- , -NHCO- and a combination of two or more of those groups. It is preferably a group.
The carbon number of Ar ⁰ is preferably 6 to 22, more preferably 6 to 18, further preferably 6 to 10, and particularly preferably a phenylene group. The preferred range of L ⁰ is synonymous with A in AR-8 described above.

From the viewpoint of i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
In formula (51), R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or difluoro. Methyl or trifluoromethyl group;
As a ^{monovalent organic group of R 50 to} R ⁵⁷ , an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a hook having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkylated group.
In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.

^{R 115} in the formula (1) represents a tetravalent organic group. The tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).
R ¹¹² is synonymous with A and has the same preferred range.

^{Specific examples of the tetravalent organic group represented by R 115} in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ has the same meaning as ^{R 115} in formula (1).

Specific examples of the tetracarboxylic dianhydride include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dichloride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1 , 4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propanedian Anhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,54-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-phenanthenetetracarboxylic dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, In addition, at least one selected from these alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms is exemplified.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also mentioned as preferable examples.

^{R 113} and R ¹¹⁴ in the formula (1) independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of R ¹¹³ and R ¹¹⁴ contains a radically polymerizable group, and it is more preferable that both contain a radically polymerizable group. Examples of the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III).

In formula (III), ^R200 represents a hydrogen atom or a methyl group, with a methyl group being more preferred.
In the formula (III), R ²⁰¹ is an alkylene group having 2 to 12 carbon atoms, −CH ₂ CH (OH) CH ₂ − or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom). ~ 12 is preferable, 1 to 6 is more preferable, and 1 to 3 are particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3). The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _{2-, and} more preferably an ethylene group, a propylene group, a trimethylene group, and -CH ₂ CH (OH) CH _2-.
Particularly preferably, R ²⁰⁰ is a methyl group and R ²⁰¹ is an ethylene group.
The polymerizable group equivalent of the radically polymerizable group (value obtained by dividing the weight average molecular weight by the number of polymerizable groups) is preferably 0.0001 or more, more preferably 0.0005 or more, and 0.001. The above is more preferable. The upper limit is preferably 0.05 or less, more preferably 0.001 or less, and even more preferably 0.005 or less. The number of polymerizable groups can be estimated from the blending amount of the raw materials at the time of synthesis.

Examples of the polyimide precursor in the present invention include aliphatic groups, aromatic groups and arylalkyl groups having 1, 2 or 3 acid groups as monovalent organic groups of ^{R 113} or R ^114. .. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group may be a hydroxyl group. That is, R ¹¹³ or R ¹¹⁴ may be a group having a hydroxyl group.
As the ^{monovalent organic group represented by R 113} or R ^114, a substituent that improves the solubility of the developing solution may be used.
R ¹¹³ or R ¹¹⁴ may be a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl in terms of solubility in an aqueous developer.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ may be a monovalent organic group. The monovalent organic group may contain a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or may be an alkyl group substituted with an aromatic group.
The alkyl group may have 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Among them, a cyclohexyl group can be mentioned from the viewpoint of achieving both high sensitivity. Further, the alkyl group substituted with an aromatic group may be a linear alkyl group substituted with an aromatic group described later.
Examples of the aromatic group include an aromatic hydrocarbon group or an aromatic heterocyclic group.
Specific examples of the aromatic hydrocarbon group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, and phenanthrene ring. , Anthracene ring, naphthalene ring, chrysen ring, triphenylene ring, fluorene ring, biphenyl ring and other groups having an aromatic hydrocarbon ring.
Examples of the aromatic heterocyclic group include substituted or unsubstituted pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, and India. Lydin ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridin ring, acrydin ring, phenanthroline Examples thereof include groups having an aromatic heterocycle such as a ring, a thiantolen ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring.

It is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or less. There is no particular upper limit, but 50% by mass or less is practical.

Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with a structural unit represented by the formula (1). Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

The structural unit represented by the formula (1) is preferably the structural unit represented by the formula (1-A).
A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ^{114 are independently synonymous with A 1} , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in equation (1), respectively, and so are the preferred ranges. is there. R ¹¹² has the same meaning as ^{R 112} in formula (5), and preferred ranges are also the same.

In the polyimide precursor, the structural unit represented by the formula (1) may be one kind, or two or more kinds. Further, the structural isomer of the structural unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of structural units in addition to the structural units of the above formula (1).

As one embodiment of the polyimide precursor in the present invention, 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the structural units are the structural units represented by the formula (1), and R. ^A polyimide precursor in which at least one (preferably both) of 113 and R ^{114 is a radically polymerizable group is exemplified.} As an upper limit, 100 mol% or less is practical.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 2000 to 500000, more preferably 5000 to 100,000, and even more preferably 1000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The degree of dispersion of the molecular weight of the polyimide precursor (weight average molecular weight / number average molecular weight) is preferably 1.5 to 3.5, more preferably 2 to 3.

The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
In the method for producing a polyimide precursor, it is preferable to use an organic solvent in the reaction. The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

In the production of the polyimide precursor, it is preferable to include a step of precipitating a solid. Specifically, the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.

<< Polybenzoxazole precursor >>
The polybenzoxazole precursor used in the present invention has a radically polymerizable group. The radically polymerizable group is preferably contained in the side chain.
The polybenzoxazole precursor more preferably contains a structural unit represented by the following formula (2).
R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group.

R ¹²¹ represents a divalent organic group. The divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and a group containing at least one of 6 to 12 is particularly preferable). Examples of the aromatic group constituting R ^{121 include R 111} of the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably derived from 4,4'-oxydibenzoyl chloride.
In formula (2), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (1), and the preferable range is also the same. R ¹²² is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group, ^{which are synonymous with R 113} and R ¹¹⁴ in the above formula (1), and the preferred range is also the same.

The polybenzoxazole precursor may contain other types of structural units in addition to the structural units of the above formula (2).
The precursor preferably contains a diamine residue represented by the following formula (SL) as another type of structural unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.

Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R ^2s. Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of ^{R 3s} , R ^4s , R ^5s , and R ^{6s is aromatic.} A group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest are hydrocarbon atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms). It is preferably an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6) carbon atoms, and may be the same or different from each other. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z moiety, preferably, the a structure is 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

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

When the precursor contains a diamine residue represented by the formula (SL) as another type of structural unit, the removal of the acid dianhydride group from the tetracarboxylic dianhydride is further carried out in terms of improving alkali solubility. It is preferable to include the tetracarboxylic dian residue remaining later as a constituent unit. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (1).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2000 to 500000, more preferably 5000 to 100,000, and even more preferably 1000 to 50000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and even more preferably 4000 to 25000.
The dispersity of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass, based on the total solid content of the composition. The above is more preferable, 50% by mass or more is further preferable, 60% by mass or more is further preferable, and 70% by mass or more is further preferable. Further, the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the composition. It is more preferably 98% by mass or less, further preferably 95% by mass or less, and even more preferably 95% by mass or less.
The photosensitive resin composition of the present invention may contain only one type of polymer precursor, or may contain two or more types of polymer precursors. When two or more types are included, the total amount is preferably in the above range.

<Thermal base generator>
The photosensitive resin composition of the present invention contains a thermal base generator. By using a thermal base generator, it is possible to generate a base species that promotes the ring closure reaction during the heating step of performing the ring closure reaction of the precursor of the heterocyclic polymer, so that the ring closure rate is further improved. On the other hand, when cyclization is promoted by the thermobase generator, the number of cross-linking points of the polymer precursor is reduced. On the other hand, in the present invention, the breakage of a part of the crosslink after cyclization is compensated by increasing the number of points of the crosslinker, which is considered to contribute to the effect of the present invention.

Examples of the thermobase generator used in the present invention include tertiary amine compounds. For example, it is a compound represented by the following formula (A1).
( ^RA1 ) N ( ^RA2 ) ₂ (A1)
In the formula, ^RA1 is an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). , 2-3), aryl group (preferably 6-22 carbon atoms, more preferably 6-18, still more preferably 6-10), arylalkyl group (preferably 7-23 carbon atoms, 7-19 carbon atoms). Is more preferable, and 7 to 11 is more preferable), and an aryl group is preferable. ^RA2 is an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms) which may have an acidic group (particularly a carboxyl group).

As the thermobase generator used in the present invention, an ammonium salt (including a pyridinium salt) is preferable. Specifically, it preferably contains a cation represented by the following formula (101) or formula (102), and a salt of this and an anion is more preferable. The anion may be attached to any part of the ammonium cation via a covalent bond (specifically, it may be betaine) or may be present outside the molecule of the ammonium cation. , Preferably present outside the molecule of the ammonium cation. The fact that the anion exists outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extramolecular anion of the cation part is also referred to as a counter anion.
In formulas (101) and (102), R ^{1 to} R ⁶ independently represent a hydrogen atom or a hydrocarbon group, and R ⁹ represents a hydrocarbon group.
However, the hydrocarbon group here means that it may have a hydroxyl group, a halogen atom, an oxo group (= O), or the like as long as the effect of the present invention is exhibited.
R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁹ , and R ⁶ and R ⁹ may be combined to form a ring, respectively.
The hydrocarbon groups of R ^{1 to} R ⁶ are alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 2 carbon atoms). 6 is more preferred, 2-3 is more preferred), aryl groups (6-22 carbon atoms are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7-23 carbon atoms are preferred). 7 to 19 is more preferable, and 7 to 11 is even more preferable).
The hydrocarbon group of R ⁹ is preferably a methylene or alkylidene group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms). The methylene group and the alkylidene group may be substituted with _{an amino group (NH 2).} This amino group may form a linking group (NH) when forming a ring. Examples of the ring formed by R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁵ and R ⁹ , and R ⁶ and R ⁹ include a 4- to 8-membered nitrogen-containing heterocycle. Examples of the compound in which R ⁵ and R ⁶ and R ⁵ and R ⁹ are bonded to form a ring in the formula (102) include diazabicycloundecene and diazabicyclononen.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).

In formulas (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ⁷ are synonymous with ^{R 1} in formula (101) or formula (102).
Among them, R ¹⁰¹ has an alkane-structured group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms) and an alkene-structured group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms are more preferable). Preferably, 2 to 3 are more preferable), an aryl structure group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, and 6 to 10 is more preferable), and an aryl structure group (particularly of a benzene ring structure) is preferable. Group) is more preferable.
In formulas (Y1-1) to (Y1-4), Ar ¹⁰¹ and Ar ¹⁰² are independently aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, and 6 to 10 are even more preferable). , N represents an integer of 1 or more, and m represents an integer of 0 to 5.
Formula (Y1-3) may also form a bicyclo ring bonded twos R ¹ is. Examples of the bicyclo compound include diazabicycloundecene, diazabicyclononen and the like.

In the present embodiment, the ammonium salt preferably has an anion having a pKa1 of 0 to 4 and an ammonium cation. The upper limit of pKa1 of the anion is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the precursor of the heterocyclic polymer can be cyclized at a lower temperature, and the stability of the photosensitive resin composition can be improved. When pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of bases can be suppressed without heating, and the stability of the photosensitive resin composition is good. When pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the precursor of the heterocyclic polymer is good.
The type of anion is preferably one selected from carboxylic acid anion, phenol anion, phosphate anion and sulfate anion, and more preferably carboxylic acid anion because both salt stability and thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to obtain a thermobase generator capable of further improving the stability, curability and developability of the photosensitive resin composition. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the photosensitive resin composition can be further improved.
In the present embodiment, the carboxylic acid anion is preferably an anion of a carboxylic acid having a pKa1 of 4 or less. The pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the photosensitive resin composition can be further improved.
Here, for pKa1, a value calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) is used.

The carboxylic acid anion is preferably represented by the following formula (X1).
In formula (X1), EWG represents an electron-attracting group.

In the present embodiment, the electron-attracting group means that Hammett's substituent constant σm shows a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present embodiment is not limited to the substituent described in the above document.
Examples of substituents in which σm shows a positive value are CF ₃ groups (σm = 0.43), CF ₃ CO groups (σm = 0.63), HC≡C groups (σm = 0.21), CH. ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH = CH group (σm = 0.21), PhCO group (σm = 0) _.34), H ₂ NCOCH 2 group (σm = 0.06), and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
In the formulas (EWG-1) to (EWG-6), R ^{x1 to} R ^x3 independently contain a hydrogen atom and an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 3). More preferably), an alkenyl group (preferably 2-12 carbon atoms, more preferably 2-6, more preferably 2-3), an aryl group (preferably 6-22 carbon atoms, more preferably 6-18 carbon atoms, 6- to 6-carbon group. 10 is more preferable), represents a hydroxyl group or a carboxyl group, Ar is an aromatic group, and an aromatic hydrocarbon group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, and 6 to 10 is even more preferable). Alternatively, an aromatic heterocyclic group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms, and examples of the hetero atom include a nitrogen atom, a sulfur atom and an oxygen atom) is preferable. Ar may have a substituent, for example, may have one to five groups of R ^X1.
Np is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.

In the present embodiment, the carboxylic acid anion is preferably represented by the following formula (XA).
Equation (XA)
In the formula (XA), L ¹⁰ is a single bond, an alkylene group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 6 carbon atoms), an alkenylene group (2 to 12 carbon atoms are preferable). Preferably, 2 to 6 are more preferred, 2-3 are more preferred), aromatic groups (aromatic hydrocarbon groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 10 are even more preferred) or. Aromatic heterocyclic groups (preferably 1-12 carbon atoms, more preferably 1-6, more preferably 1-3, heteroatoms include nitrogen, sulfur and oxygen atoms), -NR ^X- and represents a divalent linking group selected from these combinations, ^{R X} is a hydrogen atom, an alkyl group (having 1 to 12 carbon atoms, more preferably 1-6, more preferably 1 to 3), an alkenyl group ( It represents a carbon number of 2 to 12, more preferably 2 to 6, more preferably 2 to 3) or an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms). ..

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.

Specific examples of the thermobase generator include the following compounds.

The content of the thermal base generator in the photosensitive resin composition of the present invention is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
The mass ratio of the thermobase generator to the specific radically polymerizable compound (specific radically polymerizable compound / thermobase generator) is preferably 1.0 to 80. The lower limit value is preferably 1.5 or more, more preferably 2 or more, and further preferably 3 or more. The upper limit is preferably 50 or less, more preferably 20 or less, and even more preferably 10 or less. By setting this ratio within the above range, the values of elongation at break and chemical resistance are optimal.
As the thermobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Other components of the photosensitive resin composition>
The photosensitive resin composition of the present invention may contain components other than the above. Specifically, a photopolymerization initiator, a solvent, a polymerization inhibitor and the like are exemplified. It may also contain impurities derived from the raw materials used in the synthesis of the precursor of the heterocyclic polymer.

<< Photopolymerization Initiator >>
The photosensitive resin composition of the present invention preferably contains a photopolymerization initiator.
The photopolymerization initiator that can be used in the present invention is not particularly limited, and can be appropriately selected from known photopolymerization initiators. For example, a photopolymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

Since the photosensitive resin composition of the present invention contains a photopolymerization initiator, the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light. By doing so, curing due to the generated radicals occurs, and the solubility in the light-irradiated portion can be reduced. Therefore, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern that masks only the electrode portion, there is an advantage that regions having different solubilities can be easily produced according to the electrode pattern. is there.

As the photopolymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description in paragraphs 0165 to 0182 of JP-A-2016-0273557 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and 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, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

The photopolymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound has a wide exposure latitude (exposure margin) and is preferable.
As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
Preferred oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminovtan-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminovtan-2-one, and 2-acetoxy. Iminopentan-3-one, 2-acetoxyimimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one and the like.
Commercially available products include IRGACURE OXE 01, IRGACURE OXE02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PTOMER N-1919 (manufactured by ADEKA Corporation, JP2012-014502). The initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include the compounds described in JP-A-2010-262028, and the compounds 24, 36-40 described in paragraphs 0345-0348 of JP-A-2014-500852. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-2013-164471.
The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole. Selected from the group consisting of dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
More preferable photopolymerization initiators are trihalomethyltriazine compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium salt compound, benzophenone compound, acetophenone compound, and trihalo. At least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, a metallocene compound or an oxime compound is further preferable, and the oxime compound is more preferable. Especially preferable.
The photopolymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-, such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). 2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and other aromatic ketones, alkylanthraquinone and the like Kinones fused with an aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal can also be used. Further, a compound represented by the following formula (I) can also be used.
Wherein ^{(I), R 50} is an alkyl group having 1 to 20 carbon atoms, one or more alkyl groups having 2 to 20 carbon atoms which is interrupted by an oxygen atom, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, At least one of a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkoxy group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and an alkyl group having 1 to 4 carbon atoms. It is a substituted phenyl group or biphenylyl, R ⁵¹ is a group represented by the formula (II) or is the same group as ^{R 50, and R 52 to} R ⁵⁴ are each independently having 1 to 12 carbon atoms. Alkyl, alkoxy or halogen having 1 to 12 carbon atoms.
In the formula, R ^{55 to} R ⁵⁷ are the same as ^{R 52 to} R ^{54 in} the above formula (I).

Further, as the photopolymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can also be used.

The content of the photopolymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 1 with respect to the total solid content of the photosensitive resin composition of the present invention. It is ~ 5% by mass, more preferably 1 to 4% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.

<< Solvent >>
The photosensitive resin composition of the present invention preferably contains a solvent.
As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone. , Δ-Valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) )), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-) Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate) Etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy-2-methylpropionate, etc. Methyl acid and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.
Examples of ethers include 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, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.
As the sulfoxides, for example, dimethyl sulfoxide is preferable.
As the amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like are preferable.

As the solvent, a form in which two or more kinds are mixed is also preferable from the viewpoint of improving the properties of the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone. , Dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and a mixed solution composed of two or more selected from propylene glycol methyl ether acetate are preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 70% by mass, and 10 ~ 60% by mass is particularly preferable.
Only one type of solvent may be contained, or two or more types may be contained. When two or more kinds of solvents are contained, the total is preferably in the above range.

<< Migration inhibitor >>
The photosensitive resin composition preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.
The migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring), thiourea and mercapto group compounds, hindered phenolic compounds , Pyrazole acid derivative compound, hydrazide derivative compound and the like. In particular, triazole-based compounds such as triazole (for example, 1,2,4-triazole) and benzotriazole, and tetrazole-based compounds such as tetrazole and benzotriazole can be preferably used.

It is also possible to use an ion trap agent that traps anions such as halogen ions.

Examples of other migration inhibitors include rust preventives described in paragraphs 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520 can be used.

Specific examples of the migration inhibitor include 1H-1,2,3-triazole and 1H-tetrazole.

When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, preferably 0.05 to 5.0% by mass, based on the total solid content of the photosensitive resin composition. 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is further preferable.
The migration inhibitor may be only one kind or two or more kinds. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<< Polymerization inhibitor >>
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol (1,4-methoxyphenol), di-tert-butyl-paracresol, pyrogallol, p-tert-butylcatechol, parabenzoquinone (1,4-benzoquinone), and the like. Diphenyl-parabenzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine Aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5 -Nitroso-8-hydroxyquinolin, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5 (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.
In addition, the following compounds can be used (Me is a methyl group).
When the photosensitive resin composition of the present invention 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 photosensitive resin composition of the present invention.
The polymerization inhibitor may be only one kind or two or more kinds. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<< Metal Adhesive Improvement Agent >>
The photosensitive resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesiveness improving agent include a silane coupling agent.

Examples of the silane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, the compounds described in paragraphs 0063-0071 of International Publication No. 2011/080992, JP-A-2014-191252. The compounds described in paragraphs 0060 to 0061 of the above, the compounds described in paragraphs 0045 to 0052 of JP-A-2014-041264, and the compounds described in paragraph 0055 of International Publication No. 2014/0975994 can be mentioned. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Further, as the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, and more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the heterocyclic polymer precursor. When the amount is 0.1 parts by mass or more, the adhesiveness between the cured film and the metal layer after the curing process is good, and when the amount is 30 parts by mass or less, the heat resistance and mechanical properties of the cured film after the curing process are good. Become. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<< Other additives >>
The photosensitive resin composition of the present invention contains various additives such as a thermoacid generator, a sensitizing dye, a chain transfer agent, a surfactant, and a higher grade, if necessary, as long as the effects of the present invention are not impaired. Fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the photosensitive resin composition.

<<< Thermal Acid Generator >>>
The photosensitive resin composition of the present invention may contain a thermoacid generator. The thermoacid generator generates an acid by heating, promotes the cyclization of the precursor of the heterocyclic polymer, and further improves the mechanical properties of the cured film. Examples of the thermoacid generator include the compounds described in paragraph 0059 of JP2013-167742A.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the precursor of the heterocyclic polymer. By containing 0.01 part by mass or more of the thermal acid generator, the cross-linking reaction and the cyclization of the precursor of the heterocyclic polymer are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. it can. The content of the thermoacid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.
Only one type of thermoacid generator may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

<<< Sensitizing Dye >>>
The photosensitive resin composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs a specific active radiation and becomes an electron-excited state. The sensitizing dye in the electron-excited state comes into contact with a thermal base generator, a thermal radical polymerization initiator, a radical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermal base generator, the thermal radical polymerization initiator, and the radical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases. For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, preferably 0, based on the total solid content of the photosensitive resin composition of the present invention. .1 to 15% by mass is more preferable, and 0.5 to 10% by mass is further preferable. The sensitizing dye may be used alone or in combination of two or more.

<<< Chain Transfer Agent >>>
The photosensitive resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazol, etc.) can be preferably used.

When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

<<< Surfactant >>>
Each type of surfactant may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable.

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferable, more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

<<< Higher fatty acid derivative >>>
In the photosensitive resin composition of the present invention, a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition due to oxygen, and the photosensitive resin composition is dried in the process of application and drying. It may be unevenly distributed on the surface of an object.
When the photosensitive resin composition of the present invention 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 photosensitive resin composition of the present invention. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

<< Restrictions on other contained substances >>
The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of coating surface properties.

From the viewpoint of insulating properties, the metal content of the photosensitive resin composition of the present invention is preferably less than 5 parts by mass (parts per million), more preferably less than 1 parts by mass, and particularly preferably less than 0.5 parts by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition of the present invention. Methods such as filtering the raw materials constituting the photosensitive resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.

The photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and particularly preferably less than 200 mass ppm, from the viewpoint of wiring corrosiveness. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and particularly preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.

<Preparation of photosensitive resin composition>
The photosensitive resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.
Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the photosensitive resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

<Cured film, laminate, semiconductor device, and manufacturing method thereof>
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.
The cured film of the present invention is obtained by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. The laminate having two or more cured films of the present invention preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Specifically, a photosensitive resin composition layer forming step of applying the photosensitive resin composition of the present invention to a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer. And include. Preferably, the method for producing a cured film further includes a developing step of developing the photosensitive resin composition layer after the exposure step. After this development, the exposed resin layer can be further cured by including a heating step of heating (preferably heating at 50 to 450 ° C. (more preferably 50 to 250 ° C.)). As described above, when the photosensitive resin composition is used, the composition is cured by exposure in advance, and then if necessary, desired processing (for example, the following lamination) is performed, and the composition is further cured by heating. be able to.

The method for producing a laminate of the present invention includes the method for producing a cured film of the present invention. In the method for producing a laminate of the present invention, after forming a cured film according to the above-mentioned method for producing a cured film, the photosensitive resin composition is further subjected to a film forming step (layer forming step) and a heating step, or a photosensitive step. When properties are added, it is preferable to carry out the film forming step (layer forming step), the exposure step, and the developing step (if necessary, further heating step) in the above order. In particular, it is preferable to carry out each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both.
These details will be described below.

<< Membrane formation process (layer formation process) >>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the photosensitive resin composition is applied to a substrate to form a film (layered).
The type of substrate can be appropriately determined according to the application, but semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, polysilicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, thin film, and magnetic film. , Reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like are not particularly limited. In the present invention, a semiconductor-made substrate is particularly preferable, and a silicon substrate is more preferable.
Further, when the photosensitive resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a substrate.
Coating is preferable as a means for applying the photosensitive resin composition to the substrate.
Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the substrate. For a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method, a spray coating method, or an inkjet method. The method or the like is preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

<< Drying process >>
The production method of the present invention may include a step of forming the photosensitive resin composition layer, followed by a film forming step (layer forming step), and then drying to remove the solvent. The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<< Exposure process >>
The production method of the present invention may include an exposure step of exposing the photosensitive resin composition layer. Exposure is not particularly limited so long as it can be cured photosensitive resin composition, for example, it is preferable to irradiate 100~10000mJ / cm ² at an exposure energy conversion at a wavelength 365nm, 200~8000mJ / cm ² irradiated Is more preferable.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, preferably 240 to 550 nm.
In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), and (6) electron beam. The photosensitive resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and particularly preferably to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.

<< Development process >>
The production method of the present invention may include a development treatment step of performing a development treatment on the exposed photosensitive resin composition layer. By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
Development is carried out using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed. The developer preferably contains an organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
Organic solvents include, for example, ethyl acetate, -n-butyl 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, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Ethyl acid acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, 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. As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene. As the sulfoxides, dimethyl sulfoxide is preferably mentioned.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
The developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be an organic solvent having a content of 100% by mass.

The developing time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly determined, but is usually 20 to 40 ° C.
After the treatment with the developing solution, further rinsing may be performed. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the photosensitive resin composition. The rinsing time is preferably 5 seconds to 1 minute.

<< Heating process >>
The production method of the present invention preferably includes a step of heating after a film forming step (layer forming step), a drying step, or a developing step. In the heating step, the cyclization reaction of the polymer precursor proceeds. Further, although the composition of the present invention may contain a radically polymerizable compound other than the polymer precursor, curing of the radically polymerizable compound other than the unreacted polymer precursor can also proceed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 160 ° C. or higher. Is more preferable, and it is even more preferable that the temperature is 170 ° C. or higher. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. Residual stress can be relaxed.
The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the photosensitive resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is, for example, 30 higher than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually raise the temperature from a temperature as low as about 200 ° C.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
In particular, when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the polymer precursors between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

<< Metal layer forming process >>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.
As the metal layer, existing metal species can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination method thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest portion.

<< Laminating process >>
The production method of the present invention preferably further includes a laminating step.
The laminating step is the film forming step (layer forming step) and the heating step again on the surface of the cured film (resin layer) or the metal layer, or the film forming step (layer forming) on the photosensitive resin composition. Step), the exposure step, and the development processing step are a series of steps including performing the steps in the above order. Needless to say, the laminating step may further include the drying step, the heating step, and the like.
When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.
The laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, a structure such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.
That is, in the present invention, in particular, after the metal layer is provided, a film forming step (layer forming step) and a heating step of the photosensitive resin composition, or a photosensitive resin composition so as to further cover the metal layer. It is preferable that the film forming step (layer forming step), the exposure step, and the developing treatment step (if necessary, further heating step) are performed in the above order. By alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be laminated alternately.

The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the photosensitive resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.

Next, an embodiment of a semiconductor device in which the photosensitive resin composition is used as an interlayer insulating film for a rewiring layer will be described.
The semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a laminated body 101 in which a plurality of semiconductor elements (semiconductor chips) 101a to 101d are laminated is arranged on a wiring board 120.
In this embodiment, the case where the number of layers of the semiconductor element (semiconductor chip) is four is mainly described, but the number of layers of the semiconductor element (semiconductor chip) is not particularly limited, and for example, 2 It may be a layer, an 8-layer, a 16-layer, a 32-layer, or the like. Moreover, it may be one layer.

The plurality of semiconductor elements 101a to 101d are all 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) integrally provided with the through electrodes are provided on both sides of each semiconductor element.

The laminated body 101 has a structure in which a semiconductor element 101a having no through electrode and a semiconductor element 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 penetrating electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the penetrating electrode 102b adjacent thereto are connected by a metal bump 103a such as a solder bump and penetrated. 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 through 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 through electrode 102d adjacent thereto by a metal bump 103c such as a solder bump. ing.

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

The laminated body 101 is laminated on the wiring board 120.
As the wiring board 120, for example, a multilayer wiring board using an insulating substrate such as a resin substrate, a ceramics substrate, or a glass substrate as a substrate is used. Examples of the wiring board 120 to which the resin substrate is applied include a multilayer copper-clad laminate (multilayer printed wiring board) and the like.

A surface electrode 120a is provided on one surface of the wiring board 120.
An insulating film 115 on which the rewiring layer 105 is formed is arranged between the wiring board 120 and the laminated body 101, and the wiring board 120 and the laminated body 101 are electrically connected to each other via the rewiring layer 105. It is connected. The insulating film 115 is formed by using the photosensitive 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 via a metal bump 103d such as a solder bump. Further, the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
An underfill layer 110a is formed between the insulating film 115 and the laminated body 101. Further, an underfill layer 110b is formed between the insulating film 115 and the wiring board 120.

The cured film formed from the photosensitive resin composition of the present invention has both high chemical resistance and high elongation at break. Regarding chemical resistance, for example, it is preferably 500 nm / min or less, more preferably 300 nm / min or less, and further preferably 100 nm / min or less. There is no particular upper limit, but 50,000 nm / min or less is practical. The elongation at break is, for example, preferably 40% or more, more preferably 55% or more, and even more preferably 70% or more. There is no particular upper limit, but 150% or less is practical. The method for measuring chemical resistance and elongation at break conforms to the method of measurement in the examples described later.

In addition to the above, the cured film in the present invention can be widely used in various applications using polyimide or polybenzoxazole.
Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" published in November 2011 , Japan Polyimide / Aromatic Polymer Study Group / ed., "Latest Polyimide Basics and Applications", NTS, August 2010, etc. can be referred to.

The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.
Further, since polyimide and polybenzoxazole are resistant to heat, the cured film and the like in the present invention are also suitable for transparent plastic substrates for display devices such as liquid crystal displays and electronic paper, automobile parts, heat-resistant paints, coating agents, and films. Can be used for.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Synthesis of precursor composition (resin) of heterocyclic polymer>
<< Synthesis Example 1 >>
[Synthesis of polyimide precursor (A-1: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic dianhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic acid dianhydride (4,4'-oxydiphthalic acid dried at 140 ° C. for 12 hours) and 18.6 g (129 mmol) of 2- Hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, and 140 g of diglime (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain 4,4'-oxydiphthalic acid. A diester with 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes, keeping the temperature at −10 ± 4 ° C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-oxydianiline in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated in addition to 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Next, the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-1).

<< Synthesis Example 2 >>
[Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic acid dianhydride, 4,4'-oxydianiline and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic acid dianhydride (pyromellitic acid dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g. Hydroquinone, 10.7 g of pyridine, and 140 g of NMP (N-methyl-2-pyrrolidone) were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain pyromellitic acid and 2-hydroxyethyl methacrylate. Diester was produced. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes, keeping the temperature at −10 ± 4 ° C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 11.08 g (58.7 mmol) of 4,4'-oxydianiline in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated in addition to 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Next, the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-2).

<< Synthesis Example 3 >>
[Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4'-oxydiphthalic anhydride, p-phenylenediamine and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (oxydiphthalic acid dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0 0.05 g of hydroquinone, 10.7 g of pyridine and 140 g of diglime were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. did. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes, keeping the temperature at −10 ± 4 ° C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 6.34 g (58.7 mmol) of p-phenylenediamine in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated in addition to 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Then, the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-3).

<< Synthesis Example 4 >>
[Synthesis of polyimide precursor (A-4: polyimide precursor having radical polymerizable group) from pyromellitic acid dianhydride, m-trizine and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic acid dianhydride (pyromellitic acid dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g. Hydroquinone, 10.7 g of pyridine, and 140 g of NMP (N-methyl-2-pyrrolidone) were mixed and stirred at a temperature of 60 ° C. for 18 hours to obtain pyromellitic acid and 2-hydroxyethyl methacrylate. Diester was produced. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes, keeping the temperature at −10 ± 4 ° C. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. A solution of 12.46 g (58.7 mmol) of m-trizine in 100 mL of N-methylpyrrolidone was then added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated in addition to 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, added to 4 liters of water, stirred again for 30 minutes, and collected again by filtration. Next, the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor (A-4).

<< Synthesis Example 5 >>
[Synthesis of polyimide precursor composition A-5 from 4,4'-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a) shown below]
42.4 g of 4,4'-oxydiphthalic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. .. The reaction mixture was then cooled to −10 ° C. and a solution of 34.35 g of dicyclohexylcarbodiimide in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes to add 30 to the mixture. Stir for minutes. Subsequently, a solution prepared by dissolving 76.0 g of the diamine (a) shown below in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. , 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution to precipitate the polyimide precursor, which was filtered and dried at 45 ° C. for 2 days under reduced pressure. The obtained powdery polyimide precursor had a weight average molecular weight of 26500 and a number average molecular weight of 9300. The polymerizable group equivalent was about 95%.
Diamine (a)

<< Synthesis Example 6 >>
[Synthesis of polybenzoxazole precursor composition A-6 from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4'-oxydibenzoyl chloride]
28.0 g of 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was stirred and dissolved in 200 mL of N-methylpyrrolidone. Subsequently, 25.0 g of 4,4'-oxydibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and then stirring was continued for 60 minutes. 6 L of water was added to the obtained reaction solution to precipitate the polybenzoxazole precursor, and the solid was filtered and dried under reduced pressure at 45 ° C. for 2 days. The obtained powdered polybenzoxazole precursor had a weight average molecular weight of 28500 and a number average molecular weight of 9800. This polybenzoxazole precursor A-6 is an example having no radically polymerizable group.

<< Synthesis Example A-7 >>
Polyimide precursor A-7 was synthesized in the same manner as in the procedure for synthesizing the polyimide precursor of A-5, except that 2-hydroxyethyl methacrylate was not used. This polyimide precursor A-7 is an example having no radically polymerizable group.

<Preparation of photosensitive resin composition>
The resin was mixed with the components listed in the table below to prepare a coating solution of the photosensitive resin composition as a uniform solution. Each photosensitive resin composition was pressure-filtered through a UPE filter having a pore width of 0.8 μm.

<Chemical resistance>
Each photosensitive resin composition was pressure-filtered through a filter having a pore width of 0.8 μm, and then applied onto a silicon wafer by a spin coating method to form a photosensitive resin composition layer. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. ^{The photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to a nitrogen atmosphere. Below, the temperature was raised at a heating rate of 10 ° C./min and heated at the temperatures and times shown in Table 1 below to obtain a cured layer (resin layer) of the photosensitive resin composition layer.
The obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
Chemicals: Mixture of dimethyl sulfoxide (DMSO) and 25% by mass tetramethylammonium hydroxide (TMAH) solution at 90:10 (mass ratio) Evaluation conditions: Immerse the resin layer in the solution at 75 ° C. for 15 minutes before and after The film thickness was compared and the dissolution rate (nm / min) was calculated.

<Breaking elongation>
A photosensitive resin composition layer was formed on a silicon wafer by a spin coating method. The silicon wafer to which the obtained photosensitive resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of ^{500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).} The exposed photosensitive resin composition layer is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere and heated at the temperature and time shown in Table 1 below to cure the photosensitive resin composition layer. A layer (resin layer) was obtained. The resin layer was immersed in a 4.9% by volume hydrofluoric acid solution for 30 minutes, and the resin layer was peeled off from the silicon wafer to obtain a resin layer.
The breaking elongation of the resin layer was 25 ° C. and 65% RH (relative humidity) in the longitudinal and width directions of the film, with a crosshead speed of 300 mm / min, width of 10 mm, and sample length of 50 mm using a tensile tester (Tensilon). ), The measurement was performed in accordance with JIS-K6251. For the evaluation, the breaking elongations in the longitudinal direction and the width direction were measured 5 times each, and the average value of the breaking elongations in the longitudinal direction and the width direction was used. The formula for the elongation at break is according to JIS, E _b = (L _b− L ₀ ) / L ₀ × 100: E _b is the elongation at break (%), and L ₀ is the original length of the test piece (mm). ) And L _b are the length at break (mm).

<Curing conditions>
In the above chemical resistance and elongation at break tests, the temperature and time for heating and curing the polymer precursor to obtain a cured film were appropriately determined in the respective Examples and Comparative Examples. Table 1 shows the conditions.

(A) Resin (precursor of heterocyclic polymer)
A-1 to A-7: Precursor of heterocyclic polymer produced in Synthesis Examples 1 to 7.

(B) Polymerizable compound B-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) ... The above-mentioned exemplary compound B-2
The main component of B-2 is a mixture with a compound in which one of the acryloyl groups is replaced with a hydrogen atom, and a hexafunctional compound.
The other B-1, B-3 to B-14 are the compounds exemplified above in the section of the specific radically polymerizable compound.

BC1: SR-209 (manufactured by Sartmer)

(C) Photopolymerization Initiator C-1: IRGACURE OXE 01 (manufactured by BASF)
C-2: IRGACURE OXE 02 (manufactured by BASF)
C-3: IRGACURE OXE 04 (manufactured by BASF)
C-4: IRGACURE-784 (manufactured by BASF)
C-5: NCI-831 (manufactured by ADEKA CORPORATION)

(D) Thermal base generator D-1: The following compound D-2: The following compound D-3: The following compound

(E) Polymerization inhibitor E-1: 1,4-benzoquinone E-2: 1,4-methoxyphenol

(F) Migration inhibitor F-1: 1,2,4-triazole F-2: 1H-tetrazole

(G) Metal Adhesive Improvement Agent (Silane Coupling Agent)
G-1: The following compound G-2: The following compound G-3: The following compound

(H) Solvent H-1: γ-Butyrolactone H-2: Dimethyl sulfoxide H-3: N-Methyl-2-pyrrolidone H-4: Ethyl lactate

Based on the above results, the photosensitive resin composition using the specific radically polymerizable compound selected in the present invention in combination with the precursor of the heterocyclic ring-containing polymer having a radically polymerizable group and the thermobase generator The cured film formed using the above showed high chemical resistance and elongation at break, and it was found that both of these can be achieved. On the other hand, those using a bifunctional radically polymerizable compound that does not satisfy the provisions of the present invention (Comparative Examples 3) and those not using a thermobase generator (Comparative Examples 1 and 2) are inferior in chemical resistance. The result was also low for elongation at break. Further, even when the polymer precursor did not contain a polymerizable functional group (Comparative Examples 4 and 5), the chemical resistance was remarkably inferior and the elongation at break remained at a low value. As described above, in the configuration of the present invention, each component can be obtained individually only when the specific radically polymerizable compound, the heterocyclic-containing polymer precursor having a radically polymerizable group, and the thermobase generator are used at the same time. The effect was so high that it could not be achieved, and it appeared in the form of achieving both chemical resistance and elongation at break. It is understood that this is because the above three components act together on the cyclization reaction system of the polymer precursor to bring about a synergistic effect.

<Example 100>
The photosensitive resin composition of Example 1 was pressure-filtered through a filter having a pore width of 0.8 μm, and then the photosensitive resin composition was applied onto a silicon wafer by a spin coating method. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. ^{The photosensitive resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2} using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to cyclopenta. The non-developed hole was developed for 60 seconds to form a hole having a diameter of 10 μm. Then, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching the temperatures shown in Tables 1 and 2, respectively, the temperatures were maintained for the times shown in Tables 1 and 2. After cooling to room temperature, a thin copper layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer so as to cover the hole portion. Further, the same type of photosensitive resin composition is used again on the surfaces of the metal layer and the photosensitive resin composition layer, and the patterned film is heated for 3 hours from the filtration of the photosensitive resin composition in the same manner as described above. The procedure up to the above was carried out again to prepare a laminate composed of a resin layer / metal layer / resin layer.
This resin layer (interlayer insulating film for rewiring layer) was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using this interlayer insulating film for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

100: Semiconductor device 101a-101d: Semiconductor element 101: Laminated body 102b-102d: Through electrode 103a-103e: Metal bump 105: Rewiring layer 110, 110a, 110b: Underfill layer 115: Insulating film 120: Wiring board 120a: Surface electrode

Claims (27)

It contains a precursor of a heterocyclic polymer, a thermobase generator, and a radically polymerizable compound.
The precursor of the heterocyclic polymer has a radically polymerizable group and has
The radically polymerizable compound contains at least one radically polymerizable compound selected from the group consisting of a compound having four or more polymerizable functional groups and a compound having three polymerizable functional groups and having a molecular weight of 400 or less. , Photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the polymerizable functional group is a group independently selected from a vinylphenyl group, a vinyl group, and a (meth) acryloyl group. The photosensitive resin composition according to claim 1 or 2, wherein the thermobase generator has a cation represented by the formula (101) or the formula (102).
In formulas (101) and (102), R ^{1 to} R ⁶ independently represent a hydrogen atom or a hydrocarbon group, and R ⁹ represents a hydrocarbon group. The photosensitive resin composition according to any one of claims 1 to 3, wherein the precursor of the heterocyclic polymer contains a polyimide precursor or a polybenzoxazole precursor. The photosensitive resin composition according to any one of claims 1 to 3, wherein the precursor of the heterocyclic polymer contains a polyimide precursor. The photosensitive resin composition according to any one of claims 1 to 5, wherein the precursor of the heterocyclic polymer contains a structural unit represented by the following formula (1);
In formula (1), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ are. Each independently represents a hydrogen atom or a monovalent organic group. The photosensitive resin composition according to claim 6, wherein at least one of R ¹¹³ and R ^{114 contains a radically polymerizable group.} The photosensitive resin composition according to claim 6 or 7, wherein R ^{115 contains an aromatic ring.} The R ¹¹¹ is ^{represented by −Ar 0} −L ⁰ −Ar ⁰ −, each Ar ⁰ is a divalent group containing an aromatic ring independently, and L ⁰ is a single bond, even if it is substituted with a fluorine atom. A good group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, -O-, -CO-, -S-, -SO _2- , -NHCO- and two or more combinations thereof, claimed Item 2. The photosensitive resin composition according to any one of Items 6 to 8. The photosensitive resin composition according to any one of claims 6 to 9, wherein R ¹¹¹ is a group represented by the following formula (51) or formula (61);
In formula (51), R ^{50 to} R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50 to} R ⁵⁷ is a fluorine atom, a methyl group, a fluoromethyl group, or difluoro. Methyl or trifluoromethyl group;
In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups or trifluoromethyl groups, respectively. The photosensitive resin composition according to any one of claims 1 to 10, which comprises a photopolymerization initiator. The photosensitive resin composition according to any one of claims 1 to 11, wherein the mass ratio of the thermobase generator to the radically polymerizable compound is 1.0 to 80. The photosensitivity according to any one of claims 1 to 12, wherein the radical polymerizable compound is used in an amount of 2.5 parts by mass or more and 62.5 parts by mass or less with respect to 100 parts by mass of the precursor of the heterocyclic polymer. Sex resin composition. The photosensitive resin composition according to any one of claims 1 to 13, further comprising a solvent. The photosensitive resin composition according to any one of claims 1 to 14, which is subjected to development with a developing solution containing 90% by mass or more of an organic solvent. The photosensitive resin composition according to any one of claims 1 to 15, which is used for forming an interlayer insulating film for a rewiring layer. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 16. A laminated body having two or more layers of the cured film according to claim 17. The laminate according to claim 18, which has a metal layer between the cured films. The laminate according to claim 18 or 19, which has 3 to 7 layers of the cured film. A step of forming a photosensitive resin composition layer by applying the photosensitive resin composition according to any one of claims 1 to 16 to a substrate to form a photosensitive resin composition layer, and the photosensitive resin composition layer. A method for producing a cured film, which comprises an exposure step of exposing the cured film. The method for producing a cured film according to claim 21, further comprising a developing step of developing the photosensitive resin composition layer after the exposure step. The method for producing a cured film according to claim 22, wherein the developing step performs development using a developing solution containing 90% by mass or more of an organic solvent. The method for producing a cured film according to claim 22 or 23, which comprises a post-development heating step of heating the photosensitive resin composition layer at a temperature of 50 to 450 ° C. after the developing step. The method for producing a cured film according to claim 24, wherein the heating temperature is 50 to 250 ° C. The method for producing a cured film according to any one of claims 21 to 25, wherein the cured film has a film thickness of 1 to 30 μm. A semiconductor device having the cured film according to claim 17 or the laminate according to any one of claims 18 to 20.