TW201833182A - Photosensitive resin composition, cured film, laminate, method for producing cured film, method for producing laminate, and semiconductor device - Google Patents

Abstract

Provided are the following: a photosensitive resin composition with which a pattern can be formed by means of photo-radical polymerization, and with which a cured film exhibiting high breaking elongation cane be obtained; a cured film; a laminate; a method for producing a cured film; a method for producing a laminate; and a semiconductor device. The photosensitive resin composition contains: a polyimide precursor containing a repeating unit represented by formula (1); and a photo-radical polymerization initiator. In formula (1), A1 and A2 each denote an oxygen atom or NH, R111 denotes a divalent organic group, R115 denotes a tetravalent organic group, and R113 and R114 each denote a hydrogen atom or a monovalent organic group. A group represented by formula (2) is bonded to a terminal of at least one of R111, R113, R114 and R115. In formula (2), R1 denotes a hydrogen atom or a substituent group, and * denotes the bonding position to R111, R113, R114 or R115.

Description

Photosensitive resin composition, cured film, laminated body, method for producing cured film, method for producing laminated body, and semiconductor device

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

Conventionally, a protective film and an interlayer insulating film of a semiconductor element have used a polyimide resin having excellent heat resistance, electrical properties, mechanical properties, and the like. However, in recent years, with the development of high integration and large-scale semiconductor devices, it is required to reduce the thickness and size of the sealing resin package, and to use surface mounting using LOC (wafer lead) or reflow soldering.

In the production of such a semiconductor element, a photosensitive polyimide composition having a photosensitive property imparted to the polyimide resin itself is used. The reason for this is that the pattern forming process can be simplified by using a photosensitive polyimide resin composition. For example, Patent Document 1 discloses a resin composition comprising a polyimide precursor having a predetermined structure, (b) a compound which generates a radical by irradiation with actinic rays, and (c) a compound represented by the formula (4a) or (4b) and (d) a solvent. [Chemical Formula 1] (In the formula (4a), n is an integer of 3 or less. In the formula (4b), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a monovalent group. m is an integer of 9 or less.)

On the other hand, Patent Document 2 discloses a resin composition containing a compound having an ethynyl group and an epoxy compound. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2014-201695 (Patent Document 2) JP-A-2010-077192

As a result of examining the above-mentioned Patent Document 1, it was found that the elongation at break of the cured film obtained by curing the resin composition described in Patent Document 1 is insufficient. Further, Patent Document 2 does not describe the content of photoradical polymerization of a polyimide precursor, and it is impossible to form a pattern. The present invention has an object of solving the above problems, and an object of the invention is to provide a photosensitive resin composition capable of forming a pattern by photo-radical polymerization and having a high elongation at break of a cured film obtained, and a cured film and a laminate. A method for producing a body, a cured film, a method for producing a laminate, and a semiconductor device.

As a result of intensive studies, the present inventors have found that it is possible to provide a system having a carbon-carbon triple bond represented by the formula (2) by using a system which is hardened by radical polymerization. The polyimine precursor of the group is a photosensitive resin composition capable of pattern formation and having a high elongation at break of the obtained cured film. Specifically, the above problem is solved by <2> to <25> by the following mechanism <1>. <1> A photosensitive resin composition containing a polyimine precursor comprising a repeating unit represented by the following formula (1) and a photoradical polymerization initiator; Formula (1) [Chemical Formula 2] In the formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent group. An organic group; wherein a terminal represented by the following formula (2) is bonded to a terminal of at least one of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ ; Formula (2) [Chemical Formula 3] In the formula (2), R ¹ represents a hydrogen atom or a substituent, and * is a bonding site with R ¹¹¹ , R ¹¹³ , R ¹¹⁴ or R ¹¹⁵ . <2> The photosensitive resin composition according to <1>, wherein the polyimine precursor has a structure derived from a compound represented by the following formula (3); Formula (3) [Chemical Formula 4] In the formula (3), A represents a (p+q) valent group; R ¹ represents a hydrogen atom or a substituent; p represents an integer of 1 to 5; and q represents an integer of 2 or more. <3> The photosensitive resin composition according to <1>, wherein the polyimine precursor has a structure derived from a compound represented by the following formula (3a); Formula (3a) [Chemical Formula 5] In the formula (3a), A ⁰ represents a (l+m) valent group; A ¹ represents a single bond or an (n+1) valent group; R ¹ represents a hydrogen atom or a substituent; and Ar represents a (a+1) valence. The aromatic hydrocarbon group or the aromatic heterocyclic group; a, 1, m and n each independently represent an integer of 1 to 5; wherein at least one of m and n represents an integer of 2 or more. <4> The photosensitive resin composition according to <1>, wherein the polyimine precursor has a structure derived from a compound represented by the following formula (3b); Formula (3b) [Chemical Formula 6] In the formula (3b), A ⁰ represents a (l+m) valent group; R ¹ represents a hydrogen atom or a substituent; and a, l, m and n each independently represent an integer of 1 to 5; wherein, m and n are At least one of them represents an integer of 2 or more. The photosensitive resin composition according to any one of the above-mentioned formula (1), wherein a group represented by the formula (2) is bonded to at least a terminal of the R ¹¹¹ . The photosensitive resin composition according to any one of <1>, wherein the polyimine precursor further comprises a repeating unit represented by the formula (1-1); 1) [Chemical Formula 7] In the formula (1-1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or A monovalent organic group; wherein the repeating unit represented by the formula (1-1) does not contain a group represented by the above formula (2). <7> The photosensitive resin composition according to <6>, wherein R ¹¹¹ in the above formula (1-1) is represented by -Ar-L-Ar-, wherein each of Ar is independently an aromatic hydrocarbon group, L It is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, and a group containing a combination of two or more of the above. <8> The photosensitive resin composition of the above formula (1-1), wherein R ¹¹¹ in the above formula (1-1) is a group represented by the following formula (51) or (61); [Chemical Formula 8] In the formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, a fluoromethyl group or a difluoromethyl group. Or trifluoromethyl; formula (61) [chemical formula 9] In the formula (61), R ¹⁸ and R ¹⁹ each independently represent a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. The photosensitive resin composition as described in any one of the above-mentioned <1>, wherein at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group. The photosensitive resin composition of any one of the above-mentioned <1>, wherein R ¹¹⁵ is a tetravalent organic group containing an aromatic ring. The photosensitive resin composition as described in any one of <1> which further contains a radically polymerizable compound. The photosensitive resin composition of any one of <1> to <11> which further contains an alkali generator. The photosensitive resin composition according to any one of <1> to <12> which further contains a solvent. <14> The photosensitive resin composition as described in any one of <1> to <13> which is used for negative development. The photosensitive resin composition as described in any one of <1> to <14> is used for formation of the interlayer insulating film for a rewiring layer. <16> A cured film composition obtained by curing the photosensitive resin composition according to any one of <1> to <15>. <17> A laminate having two or more cured films of <16>. <18> The laminate according to <17>, wherein a metal layer is provided between the cured films. <19> A method for producing a cured film, which comprises the use of the photosensitive resin composition according to any one of <1> to <15>. <20> The method for producing a cured film according to <19>, comprising: a process for forming a photosensitive resin composition layer, applying the photosensitive resin composition to a substrate to form a layer; and exposing the above process The photosensitive resin composition layer is subjected to exposure; and a development processing process is performed to develop the photosensitive resin composition layer exposed as described above. <21> The method for producing a cured film according to <20>, wherein the development treatment is a negative development treatment. <22> The method for producing a cured film according to <20>, wherein the developed photosensitive resin composition layer is heated at a temperature of 50 to 450 ° C after the development treatment process. Process. The method for producing a cured film according to any one of the above aspects, wherein the cured film has a thickness of 1 to 30 μm. In the method for producing a cured film according to any one of the aspects of the present invention, the method for producing a cured film according to any one of the items of the present invention, wherein after the cured film is formed, the photosensitive resin composition layer is further formed into a process, The exposure process and the above development process are sequentially performed 2 to 5 times. <25> A semiconductor device comprising the cured film according to <16> or the laminate according to <17> or <18>. [Effect of the invention]

According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a pattern by photo-radical polymerization, and having a high elongation at break of the obtained cured film, and a method for producing a cured film, a laminate, a cured film, and a laminate Body manufacturing method and semiconductor device.

The description of the constituent elements of the present invention described below may be performed based on representative embodiments of the present invention, but the present invention is not limited to the embodiments. Regarding the labeling of the group (atomic group) in the present specification, the unsubstituted and unsubstituted labeling group is not included, and includes those having no substituent and 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 "exposure" is not particularly limited, and in addition to exposure by light, the drawing by a particle beam such as an electron beam or an ion beam is also included in the exposure. In addition, as the light to be used for exposure, an actinic ray or a radiation such as a far-line ultraviolet ray, an extreme ultraviolet ray (EUV light), an X-ray, or an electron beam typified by a bright line spectrum of a mercury lamp or an excimer laser is generally used. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", and "(meth)acrylic" means "acrylic" and "methacrylic". "either or both of them, "(meth)acrylylene" means either or both of "acryloyl" and "methacryl". In this specification, the term "process" is not only an independent process, but is also included in the term if the effect expected for the process can be achieved even if it cannot be clearly distinguished from other processes. In the present specification, the solid content concentration means the mass percentage of the components other than the solvent with respect to the total mass of the composition. Further, the solid content concentration means a concentration at 25 ° C unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined by gel permeation chromatography (GPC measurement), and are defined as styrene equivalent values unless otherwise specified. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be, for example, HLC-8220 (manufactured by TOSOH CORPORATION), and the protective column HZ-L, TSKgel Super HZM-M, TSKgel Super can be used as a column. HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were obtained. Unless otherwise specified, the eluent is measured by THF (tetrahydrofuran). Further, unless otherwise specified, the detector is a wavelength 254 nm detector using UV rays (ultraviolet rays).

<Photosensitive Resin Composition> The photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as "the composition of the present invention") is characterized by containing a polyfluorene comprising a repeating unit represented by the following formula (1) Amine precursor and photoradical polymerization initiator. By adopting such a structure, a pattern can be formed by photo-radical polymerization, and a cured film having a high elongation at break can be obtained. Further, when a plurality of layers of the resin layer formed of the composition of the present invention are laminated, the adhesion between the layers becomes a problem. Specifically, in addition to the adhesion between the resin layer and the resin layer, when a metal layer is provided between the resin layer and the resin layer, the adhesion between the resin layer and the metal layer is also required. In the present invention, the adhesion between the layers can be improved by bonding the polyimide precursor to the group represented by the formula (2). Although this mechanism is not presumed, it is presumed that the reason is that the group represented by the formula (2) is consumed after exposure, and the reactivity in the interlayer is improved at the time of exposure or thermal hardening in the case of multi-layer lamination. . Further, when the photosensitive resin composition is used in the formation of the resin layer of the multilayer laminate, it is desirable that the photosensitive resin composition has a wide exposure latitude, but the photosensitive resin composition of the present invention can also increase the exposure latitude. . Formula (1) [Chemical Formula 10] In the formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent group. An organic group; wherein a terminal represented by the following formula (2) is bonded to a terminal of at least one of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ ; Formula (2) [Chemical Formula 11] In the formula (2), R ¹ represents a hydrogen atom or a substituent, and * is a bonding site with R ¹¹¹ , R ¹¹³ , R ¹¹⁴ or R ¹¹⁵ .

<<Polyimine precursor>> The polyimine precursor used in the present invention contains a repeating unit represented by the formula (1). Further, a repeating unit other than the repeating unit represented by the formula (1) may be further included. Hereinafter, the contents of these will be described in detail.

<<<Repeating unit represented by the formula (1)>>> The polyimine precursor used in the present invention contains a repeating unit represented by the formula (1). Formula (1) [Chemical Formula 12] In the formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent group. An organic group; wherein a terminal represented by the following formula (2) is bonded to a terminal of at least one of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ ; Formula (2) [Chemical Formula 13] In the formula (2), R ¹ represents a hydrogen atom or a substituent, and * is a bonding site with R ¹¹¹ , R ¹¹³ , R ¹¹⁴ or R ¹¹⁵ .

Here, "the group represented by the following formula (2) is bonded to the terminal of at least one of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ " means that it is not contained in R ¹¹¹ as in the case of a so-called linking group. The interior of the group, but R ¹¹³ and/or R ¹¹⁴ itself is a group represented by the formula (2), or at least one of the hydrogen atoms constituting R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ is 2) The case where the indicated group is replaced. In the present invention, among R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ , a group represented by the formula (2) is preferably bonded to at least the terminal of R ¹¹¹ . Further, in the examples of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ , at least one of R ¹¹³ and R ¹¹⁴ is bonded to the terminal group represented by the formula (2). In the present embodiment, a group represented by the formula (2) or a radical polymerizable group is preferably bonded to the terminal of the other of R ¹¹³ and R ¹¹⁴ . Further, in the case of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ , at least the group represented by the formula (2) is bonded to the end of R ¹¹⁵ . In the present embodiment, R ¹¹⁵ is an aromatic hydrocarbon group having a substituent, and the substituent of the aromatic hydrocarbon group is a group represented by the formula (2) itself, or a substituent of the aromatic hydrocarbon group is further represented by the formula (2) Substituting for the group is preferred. In the present invention, it is preferred to include 1 to 5 groups represented by the formula (2) in a repeating unit represented by the formula (1), preferably 1 to 3, more preferably one or two. Preferably.

R ¹ represents a hydrogen atom or a substituent, a hydrogen atom, an alkyl group or an aryl group is preferred, a hydrogen atom or an alkyl group is more preferred, and a hydrogen atom is further preferred. When R ¹ is a substituent, the following substituent T is exemplified, and a substituent amount (the mass per unit of the substituent portion per unit g, unit g) of 15 to 300 is preferable, and the amount of the formula is A substituent of 15 to 100 is more preferable. The above substituent is preferably composed only of an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom and a nitrogen atom.

(Substituent T) an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkyne having 2 to 30 carbon atoms) An aryl group (preferably an aryl group having 6 to 30 carbon atoms), an amine group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms) a aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group, a decyl group (preferably a fluorenyl group having 1 to 30 carbon atoms), an alkoxycarbonyl group (preferably An alkoxycarbonyl group having 2 to 30 carbon atoms, an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 30 carbon atoms), a decyloxy group (preferably a decyloxy group having 2 to 30 carbon atoms), Amidino group (preferably a decylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), or an aryloxycarbonylamino group (more) Preferably, it is an aryloxycarbonylamino group having 7 to 30 carbon atoms, an aminesulfonyl group (preferably an amidoxime group having a carbon number of 0 to 30), an amine formazan group (preferably having a carbon number of 1 to 30) An amidinoyl group, an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), An arylthio group (preferably having a carbon number of 1 to 30), an alkylsulfonyl group (preferably having a carbon number of 1 to 30), an arylsulfonyl group (preferably having a carbon number of 6 to 30), and a heteroarylsulfonyl group. Sulfhydryl group (preferably having a carbon number of 1 to 30), alkylsulfinyl group (preferably having a carbon number of 1 to 30), arylsulfinyl group (preferably having a carbon number of 6 to 30), and a heteroaryl group. a sulfinyl group (preferably having a carbon number of 1 to 30), a urea group (preferably having a carbon number of 1 to 30), a guanidinium phosphate group (preferably having a carbon number of 1 to 30), a hydroxyl group, a mercapto group, a halogen atom, A cyano group, an alkylsulfinylene group, an arylsulfinyl group, a fluorenyl group, an imido group, a heteroaryl group (preferably having a carbon number of 1 to 30), or a tetrahydrofuranyl group. When the groups are groups which can be further substituted, they may have a substituent. The substituent which is described in the above-mentioned substituent T is mentioned as a substituent.

The polyimine precursor used in the present invention preferably has a structure derived from a compound represented by the following formula (3). Formula (3) [Chemical Formula 14] In the formula (3), A represents a (p+q) valent group; R ¹ represents a hydrogen atom or a substituent; p represents an integer of 1 to 5, and q represents an integer of 2 or more. In the compound represented by the formula (3), the guanamine group is reacted with a carboxylic acid or an anhydrous carboxylic dianhydride which is a raw material of the polyimide precursor, and is preferably introduced into the polyimide precursor. . Specifically, a part of the NH-R ¹¹¹ -NH of the formula (1) is preferably a compound represented by the formula (3).

In the formula (3), examples of the (p+q) valent group represented by A include a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, and -OCO. -, -SO ₂ - or a group comprising a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be cyclic or non-cyclic. Further, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may or may not have a substituent. The substituent T mentioned above can be mentioned as a substituent. Further, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a single ring or a fused ring, but a single ring is preferred. Examples of the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group, an anthracene ring group, an indanyl group, an anthracene group, and a tetrahydronaphthyl group. The heterocyclic group may be a single ring or a fused ring. As the heterocyclic group, a 5-membered ring or a 6-membered ring is preferred. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Further, examples of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of the heterocyclic group include a furanyl group, a thiophene ring group, a pyrrole ring group, a pyrancyclo group, a thiopyranyl group, a pyridine ring group, an oxazole ring group, a thiazole ring group, an imidazole ring group, a pyrimidine ring group, and the like. Triazine ring group, anthracene ring group, quinoline ring group, anthracene ring group, benzimidazole ring group, benzothiazole ring group, quinoxaline ring group and carbazole ring group. Specific examples of the (p+q) valent group include a group in which one or two or more of the following structural units are combined (a ring structure can be formed). R represents a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is preferred.

[Chemical Formula 15]

The (p+q) valence group represented by A is composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom, and a nitrogen atom, and the formula (the mass per unit of the A moiety per unit) g) is preferably from 30 to 900, more preferably from 50 to 600.

In the formula (3), p represents an integer of 1 to 5. q represents an integer of 2 or more. An integer of p to 1 to 4 is preferable, an integer of 1 to 3 is more preferable, 1 or 2 is further more preferable, and 1 is further more preferable. An integer of 2 to 4 is preferred, 2 or 3 is more preferred, and 2 is further preferred. When the p system is 2 or more, a plurality of R ¹ may be the same or different.

In the formula (3), R ¹ represents a hydrogen atom or a substituent. Same as R (2) is R (3) in the preferred range of formula ¹ formula ^1.

In the present invention, the polyimine precursor has a structure in which the compound represented by the following formula (3a) is more preferable. That is, the compound represented by the formula (3) is more preferably represented by the formula (3a). Formula (3a) [Chemical Formula 16] In the formula (3a), A ⁰ represents a (l+m) valent group; A ¹ represents a single bond or an (n+1) valent group; R ¹ represents a hydrogen atom or a substituent; and Ar represents a (a+1) valence. The aromatic hydrocarbon group or the aromatic heterocyclic group; a, 1, m and n each independently represent an integer of 1 to 5; wherein at least one of m and n represents an integer of 2 or more.

In the formula (3a), as the (l+m) valent group represented by A ⁰ , a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, - may be mentioned. OCO-, -SO ₂ - or a group comprising a combination thereof, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, -SO ₂ - or a combination thereof The group is more preferably, and -NH-, -CO- or a group containing a combination thereof is further preferred. R represents a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is preferred. The details of the hydrocarbon group and the heterocyclic group are the same as those described for the (p+q) valence group represented by the above A, and the preferred ranges are also the same.

In the formula (3a), examples of the (n+1)-valent group represented by A ¹ include a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, - OCO -, - SO ₂ - or a group of a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is preferred. The details of the hydrocarbon group and the heterocyclic group are the same as those described for the (p+q) valence group represented by the above A. The (n+1)-valent group represented by A ¹ is preferably a hydrocarbon group or a heterocyclic group, more preferably a hydrocarbon group, more preferably an aromatic hydrocarbon group, and a benzene ring group is further preferred.

In the formula (3), R ¹ represents a hydrogen atom or a substituent. Same as R (2) is R (3) in the preferred range of formula ¹ formula ^1.

In the formula (3a), an Ar-based (a+1)-valent aromatic hydrocarbon group is preferred, and a benzene ring group is more preferred.

In the formula (3a), a, l, m and n each independently represent an integer of 1 to 5. Here, at least one of m and n represents an integer of 2 or more. When l and m are each 2 or more, a plurality of R ¹ , Ar and A ¹ may be independently the same or different.

A is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and further preferably 1 is further preferred. l is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and further preferably 1 is further preferred. The m-systems 1 to 4 are preferred, the 1-3 is more preferred, the 1 or 2 is further preferred, and the 1 is further preferred. n is preferably 1 to 4, more preferably 2 to 4, further preferably 2 or 3, and further preferably 2. Further, (l+m) is preferably 2 to 6, 2 to 5 is further more preferred, 2 or 3 is further preferred, and 2 is particularly preferred.

In the present invention, the structure in which the polyimine precursor has a compound represented by the following formula (3b) is further preferable. That is, the compound represented by the formula (3) is further preferably represented by the formula (3b). Formula (3b) [Chemical Formula 17] In the formula (3b), A ⁰ represents a (l+m) valent group; R ¹ represents a hydrogen atom or a substituent; and a, l, m and n each independently represent an integer of 1 to 5; wherein, m and n are At least one of them represents an integer of 2 or more. In the formula (3b), A ⁰ , R ¹ , a, l, m and n are each independently defined as A ⁰ , R ¹ , a, l, m and n in the formula (3a), and the preferred range is also the same. .

Hereinafter, the compound represented by the formula (3) used in the present invention is exemplified. Of course, the invention is not limited to these. [Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

A ¹ and A ² in the formula (1) each independently represent an oxygen atom or NH, and an oxygen atom is preferred. R ¹¹¹ in the formula (1) 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 hydrocarbon group, a linear aliphatic group having 2 to 20 carbon atoms, and a branched fatty group having 3 to 20 carbon atoms. a group, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group containing a combination thereof, is preferable, and a group containing an aromatic hydrocarbon group having 6 to 20 carbon atoms is Better.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor are linear or branched aliphatic, cyclic aliphatic or aromatic diamine. The diamine may be used singly or in combination of two or more. The diamine is preferably a compound represented by the formula (3). When R ¹¹¹ is not derived from the compound represented by the formula (3), R ¹¹¹ is the same as R ¹¹¹ in the repeating unit represented by the formula (1-1) described later, and the preferred range is also the same.

R ¹¹⁵ in the formula (1) represents a tetravalent organic group, and as the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more good. Formula (5) [Chemical Formula 22] In the formula (5), R ¹¹² is a single bond or an aliphatic hydrocarbon group selected from a carbon number of 1 to 10 which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ -, -NHCO- And a group thereof, preferably a single bond selected from alkyl groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO ₂ - More preferably, the group is selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ - The divalent group in the group is further preferred.

Formula (6) [Chemical Formula 23]

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. The tetracarboxylic dianhydride may be used singly or in combination of two or more. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O). Formula (O) [Chemical Formula 24] In the formula (O), R ¹¹⁵ represents a tetravalent organic group. R ¹¹⁵ is the same as defined for R ¹¹⁵ of the formula (1).

Specific examples of the tetracarboxylic dianhydride are exemplified by pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 3,3',4,4'. -diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxodiphthalic dianhydride, 2,3,6, 7-naphthalenetetracarboxylic dianhydride, 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis (2) , 3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4, 4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10- Terpene tetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic acid Anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane Anhydride, pyromellitic dianhydride and derivatives thereof alkyl having 1 to 6 and / or alkoxy having 1 to 6 derivative of at least one.

Further, preferred examples thereof include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below. [Chemical Formula 25]

In the formula (1), R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and at least one of R ¹¹³ and R ¹¹⁴ preferably contains a radical polymerizable group, and both of them contain a radical polymerizable group. It is better. The radically polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferred example thereof is a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III).

[Chemical Formula 26]

In the formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, and a methyl group is more preferable. In the formula (III), R ²⁰¹ is a linking group, and -CH ₂ -, -O-, -CO- or a group containing a combination thereof is preferred.

From the viewpoint of solubility for an aqueous developing solution, R ¹¹³ or R ¹¹⁴ may be a monovalent organic group other than a hydrogen atom or a radical polymerizable group. For the monovalent organic group other than the radical polymerizable group, the description of paragraph 0087 of JP-A-2016-027357 can be referred to, and the contents are incorporated in the present specification.

Further, it is also preferred that the polyimine precursor has a fluorine atom in the structural unit. The content of the fluorine atom in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

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

The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A). That is, at least one of the polyimine precursors used in the present invention has a repeating unit precursor represented by the formula (1-A). By setting it as such a structure, the magnitude|size of exposure latitude can further expand. Formula (1-A) [Chemical Formula 27] In the formula (1-A), A ¹ and A ^{2 each} represent an oxygen atom, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, and R ¹¹³ And at least one of R ¹¹⁴ contains a group of a polymerizable group, and a polymerizable group is preferred. Here, a group represented by the above formula (2) is bonded to the terminal of at least one of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹² .

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are each independently the same as defined for A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in the formula (1), and the preferred ranges are also the same. It defined the same as R ¹¹² (5) and in formula R ^112, preferred ranges are also the same.

The polyimine precursor may contain only one repeating structural unit represented by the formula (1), or may contain two or more kinds. Further, a structural isomer of a repeating unit represented by the formula (1) may be contained.

<<<Other Repeating Units>>> The polyimine precursor used in the present invention may contain a repeating unit other than the repeating unit represented by the formula (1), and includes a repeating unit other than the formula (1) The repeating unit is preferred, and the repeating unit represented by the formula (1-1) is further preferred. Formula (1-1) [Chemical Formula 28] In the formula (1-1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or A monovalent organic group; wherein the repeating unit represented by the formula (1-1) does not contain a group represented by the above formula (2).

^{A 1, A 2, R 115} , R 113 and R ¹¹⁴ in formula (1-1) each independently have the formula A ^1, A ^2, the same as R ^115, R ¹¹³ and R ¹¹⁴ defined in (1), more The range is also the same. When the polyimine precursor used in the present invention has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (1-1), A ¹ , A ² , R in the formula (1) ¹¹⁵ , R ¹¹³ and R ¹¹⁴ may be the same as or different from A ¹ , A ² , R ¹¹⁵ , R ¹¹³ and R ¹¹⁴ in the formula (1-1).

R ¹¹¹ in the formula (1-1) 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 hydrocarbon group, a linear aliphatic group having 2 to 20 carbon atoms, and a branched fatty group having 3 to 20 carbon atoms. a group, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group containing a combination thereof, is preferable, and a group containing an aromatic hydrocarbon group having 6 to 20 carbon atoms is Better.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include a linear or branched aliphatic, cyclic aliphatic or aromatic diamine. The diamine may be used singly or in combination of two or more. Specifically, it contains a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group containing a combination thereof. A diamine is preferable, and a diamine containing a group having an aromatic hydrocarbon group of 6 to 20 carbon atoms is more preferable. Examples of the aromatic hydrocarbon group include the following.

[Chemical Formula 29] Wherein A is a single bond or an aliphatic hydrocarbon group selected from carbon atoms of 1 to 10 which may be substituted by a fluorine atom, -O-, -C(=O)-, -S-, -S(=O) ₂ - Preferred groups in the group -NHCO- and combinations thereof are a single bond selected from an alkyl group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, -O-, -C(=O)-, - The group in S-, -SO ₂ - is more preferably selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ - and -C(CH ₃ The divalent group in the group of ₂ - is further preferred.

Specific examples of the diamines can be referred to in paragraph 0003 of JP-A-2016-027357, and the contents are incorporated in the present specification.

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

[Chemical Formula 30]

[Chemical Formula 31]

Further, as a preferred example, a diamine having at least two or more alkylene glycol units in the main chain may be mentioned. It is preferably a diamine containing a total of two or more ethylene glycol chains and propylene glycol chains in one molecule, and more preferably a diamine containing no aromatic ring. 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 (registered trademark) EDR-176, JEFFAMINE (registered trademark) D-200, JEFFAMINE (registered trademark) D-400, JEFFAMINE (registered trademark) D-2000, JEFFAMINE (registered trademark) D-4000 (above is the trade name) , manufactured by HUNTSMAN INTERNATIONAL LLC., 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-yl, 1-(1-(1-(2) -Aminopropoxy)propan-2-yl)oxy)propan-2-amine group, etc., but is not limited thereto. The following shows JEFFAMINE (registered trademark) KH-511, JEFFAMINE (registered trademark) ED-600, JEFFAMINE (registered trademark) ED-900, JEFFAMINE (registered trademark) ED-2003, JEFFAMINE (registered trademark) EDR-148, JEFFAMINE ( Registered trademark) Structure of EDR-176.

[Chemical Formula 32]

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

From the viewpoint of the flexibility of the obtained cured film, R ¹¹¹ in the formula (1-1) is preferably represented by -Ar-L-Ar-. Wherein Ar is independently an aromatic hydrocarbon group, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO- And a group comprising a combination of two or more of the above. The Ar-based phenyl group is preferred, and the L-based aliphatic hydrocarbon group having 1 or 2 carbon atoms, -O-, -CO-, -S- or -SO ₂ -, which may be substituted by a fluorine atom, is further preferred. Among them, an aliphatic hydrocarbon group alkylene group is preferred.

From the viewpoint of the i-ray transmittance, R ¹¹¹ in the formula (1-1) is preferably a group represented by the following formula (51) or (61). In particular, the group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability. Formula (51) [Chemical Formula 33] In the formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, a fluoromethyl group or a difluoromethyl group. Or trifluoromethyl. Examples of the monovalent organic group of R ¹⁰ to R ¹⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a carbon number of 1 to 10 (preferably, carbon numbers 1 to 6). a fluorinated alkyl group or the like. Formula (61) [Chemical Formula 34] In the formula (61), R ¹⁸ and R ¹⁹ each independently represent a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. Examples of the diamine compound which imparts a structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl and 2,2'-bis(trifluoromethyl)-4,4. '-Diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. These may be used alone or in combination of two or more.

When the polyimine precursor contains a repeating structural unit represented by the formula (1-1), it may contain only one repeating structural unit represented by the formula (1-1), or may contain two or more kinds. Further, a structural isomer of a repeating unit represented by the formula (1-1) may be contained.

An embodiment of the polyimine precursor of the present invention includes a repeating unit represented by the formula (1) and a repeating unit represented by the formula (1-1), and the repeating unit represented by the formula (1) The total of the repeating units represented by the formula (1-1) is preferably 80% by mass or more, and more preferably 90% by mass or more based on the total repeating units. When the polyimine precursor used in the present invention contains a repeating unit represented by the formula (1) and a repeating unit represented by the formula (1-1), the repeating unit represented by the formula (1) and the formula (1) The molar ratio of the repeating unit represented by 1-1) is preferably from 0.02 to 1:50, more preferably from 1:0.1 to 1:20.

<<<Characteristics of Polyimine Precursor>>> In the polyimine precursor used in the present invention, the amount of the group represented by the formula (2) is 0.05 with respect to the polyamidene precursor 1 g. It is preferably 5.05.0 mmol, more preferably 0.1 to 2.5 mmol. In the present invention, the ratio of the number of radical polymerizable groups contained in the photosensitive resin composition to the number of groups represented by the formula (2) is the number of radical polymerizable groups: from the formula (2) The number of groups indicated is preferably from 1:0.05 to 2.0, more preferably from 1:0.1 to 1.0. The weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, still more preferably from 10,000 to 50,000. Further, the number average molecular weight (Mn) is preferably from 800 to 250,000, more preferably from 2,000 to 50,000, still more preferably from 4,000 to 25,000. The degree of dispersion is preferably from 1.5 to 2.5.

Specific examples of the polyimide intermediate precursor which can be used in the present invention are shown below. Of course, the invention is not limited to these. When the polyimine precursor shown below is a copolymer, the molar ratio of the repeating unit on the left side and the repeating unit on the right side is appropriately set in the range of 1:0.02 to 50. [Chemical Formula 35]

[Chemical Formula 36]

[Chemical Formula 37]

[Chemical Formula 38]

[Chemical Formula 39]

[Chemical Formula 40]

[Chemical Formula 41]

The photosensitive resin composition of the present invention preferably contains 20 to 100% by mass of a polyimine precursor, and more preferably 50 to 99% by mass, and more preferably 60 to 98% by mass, based on the total solid content of the composition. More preferably, it is particularly preferably contained in an amount of 70 to 95% by mass. The polyimine precursor may be contained alone or in combination of two or more. When two or more types are contained, the total amount is preferably in the above range.

<<<Production of Polyimine Precursor>>> The polyimine precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. It is preferably obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting it with a diamine. In the method for producing a polyimide precursor, it is preferred to use an organic solvent in the reaction. The organic solvent may be one type or two or more types. The organic solvent can be appropriately set depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

In the case of producing a polyimide precursor, in order to further improve storage stability, it is preferably blocked with a blocking agent such as an acid dianhydride, a monocarboxylic acid, a monofluorene compound or a mono-active ester compound. Among these, a monoamine is more preferable, and preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyl group. Quinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-amine Naphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-amine Naphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amine Benzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonate Acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4 - Aminothiophenols and the like. These may be used in combination of two or more kinds, and a plurality of different terminal groups may be introduced by reacting a plurality of blocking agents.

When the polyimine precursor is produced, a process for depositing a solid may be included. Specifically, solid precipitation can be carried out by precipitating the polyimine precursor in the reaction liquid in water and dissolving in a solvent such as tetrahydrofuran which can dissolve the polyimide precursor. Then, the polyimide precursor is dried to obtain a powdery polyimide intermediate.

<<Photoradical polymerization initiator>> The composition of the present invention contains a photoradical polymerization initiator. The photoradical polymerization initiator which can be used in the present invention is not particularly limited, and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator which is photosensitive to light from the ultraviolet region to the visible region is preferred. Further, it is possible to produce some action with a photoexcited sensitizer and to generate an active radical active agent. The photoradical polymerization initiator preferably contains at least one compound having an absorption coefficient of at least about 50 moles in the range of about 300 to 800 nm, preferably 330 to 500 nm. The molar absorption coefficient of the compound can be measured by a known method. For example, it is preferred to carry out the measurement at a concentration of 0.01 g/L by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian Co., Ltd.) using an ethyl acetate solvent.

The composition of the present invention contains a photoradical polymerization initiator, and the composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and is caused by radicals by irradiation of light. It is hardened, so that the solubility in the light-irradiating portion can be lowered. Therefore, for example, it is advantageous in that the photosensitive resin composition layer is exposed through a light mask having a pattern of only the electrode portions, whereby regions having different solubility can be easily produced depending on the pattern of the electrodes.

As a photoradical polymerization initiator, a known compound can be used arbitrarily, and examples thereof include a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having a oxadiazole skeleton, a compound having a trihalomethyl group, etc.). a mercaptophosphine compound such as a mercaptophosphine oxide, an antimony compound such as a hexaarylbisimidazole or an anthracene derivative, an organic peroxide, a sulfur compound, a ketone compound, an aromatic onium salt, a ketoxime ether, or an aminoacetophenone compound. , hydroxyacetophenone, azo compound, azide compound, metallocene compound, organoboron compound, iron aromatic hydrocarbon complex, and the like. For the details of the above, the descriptions of paragraphs 0165 to 0182 of JP-A-2016-027357 can be referred to, and the contents are incorporated in the present specification.

The ketone compound is, for example, a compound described in paragraph 0087 of JP-A-2015-087611, and the contents are incorporated in the present specification. In the commercial product, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be suitably used.

As the photoradical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and a mercaptophosphine compound can also be suitably used. More specifically, for example, an amino acetophenone-based starter described in JP-A-10-291969 and a sulfhydryl phosphine oxide-based starter described in Japanese Patent No. 4,258,899 can be used. As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (product names: all manufactured by BASF Corporation) can be used. As the amino acetophenone-based initiator, IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) which are commercially available can be used. Further, as the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179, which has a maximum absorption wavelength and a wavelength source such as 365 nm or 405 nm, can be used. Examples of the mercaptophosphine-based initiator include 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide. Further, IRGACURE-819 or IRGACURE-TPO (trade name: all manufactured by BASF Corporation) which is a commercial item can be used. As the metallocene compound, IRGACURE-784 (manufactured by BASF Corporation) or the like is exemplified.

As the photoradical polymerization initiator, a ruthenium compound is more preferred. The exposure latitude can be further effectively improved by using a ruthenium compound. Among the ruthenium compounds, the exposure latitude (exposure margin) is wide, and it also functions as a photobase generator, which is particularly preferable. As a specific example of the ruthenium compound, a compound described in JP-A-2001-233842, a compound described in JP-A-2000-80068, and a compound described in JP-A-2006-342166 can be used. . Preferred examples of the ruthenium compound include a compound of the following structure: 3-benzylideneoxyimidobutan-2-one, 3-ethyloxyiminobutane-2-one, and 3 - propionyloxyiminobutan-2-one, 2-ethoxymethoxyiminopentan-3-one, 2-ethyloxyimino-1-phenylpropan-1-one , 2-benzylideneoxyimido-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy Iminoamino-1-phenylpropan-1-one and the like. [Chemical Formula 42] In the commercial product, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, BASF), ADEKA OPTOMER N-1919 (made by ADEKA CORPORATION, JP-A-2012-14052) can also be suitably used. The photoradical polymerization initiator 2) described in the publication. Further, TR-PBG-304 (manufactured by Changzhou Strong Electronic New Material Co., Ltd.), ADECARARKLS NCI-831, and ADELAARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. Further, DFI-091 (manufactured by DAITO CHEMIX Co., Ltd.) can also be used. Further, a ruthenium compound having a fluorine atom can also be used. Specific examples of the ruthenium compound include the compounds described in JP-A-2010-262028, and the compounds 24 and 36 to 40 described in paragraphs 0345 to 0358 of JP-A-2014-500852. The compound (C-3) and the like described in paragraph 0101 of JP-A-2013-164471. The ruthenium compound having a specific substituent as shown in JP-A-2007-269779, and the sulfonium compound having a thioaryl group as shown in JP-A-2009-191061, may be mentioned. Wait.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is selected from the group consisting of a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, and a mercapto group. Phosphine compound, phosphine oxide compound, metallocene compound, hydrazine compound, triaryl imidazole dimer, sulfonium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and derivative thereof, cyclopentadienyl group a compound of the group consisting of a benzene-iron complex and a salt thereof, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound. More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-amino ketone compounds, mercaptophosphine compounds, phosphine oxide compounds, metallocene compounds, ruthenium compounds, triaryl imidazole dimers, ruthenium a salt compound, a benzophenone compound, an acetophenone compound, selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an anthraquinone compound, a triaryl imidazole dimer, and a benzophenone compound Further, at least one compound is further preferably used, and a metallocene compound or a ruthenium compound is further preferably used, and a ruthenium compound is still more preferable. Further, the photoradical polymerization initiator can also use N such as benzophenone or N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone). N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, An anthracene such as an aromatic ketone such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-acetone-1 or an alkyl hydrazine, which is condensed with an aromatic ring, A benzoin compound such as a benzoin alkyl ether, a benzoin compound such as benzoin or an alkyl benzoin, or a benzyl derivative such as benzyldimethylketal. Further, a compound represented by the following formula (I) can also be used. [Chemical Formula 43] In the formula (I), R ⁵⁰ is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, or a phenyl group. An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and a carbon number interrupted by one or more oxygen atoms 2 a phenyl group or a biphenyl group in which at least one of the alkyl group of -18 and the alkyl group having 1 to 4 carbon atoms is substituted, and R ⁵¹ is a group represented by the formula (II) or a group similar to R ⁵⁰ . R ⁵² to R ⁵⁴ each independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a halogen. [Chemical Formula 44] In the formula, R ⁵⁵ to R ⁵⁷ are the same as R ⁵² to R ^{54 of the} above formula (I).

Further, as the photoradical polymerization initiator, the compound described in paragraphs 0048 to 0055 of International Publication WO2015/125469 can also be used.

The content of the photoradical polymerization initiator is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass, even more preferably from 1 to 15% by mass, based on the total solid content of the composition of the present invention, further It is preferably from 1 to 10% by mass. The photoradical polymerization initiator may be contained alone or in combination of two or more. When two or more kinds of photoradical polymerization initiators are contained, the above range is preferred.

<<Thermal radical polymerization initiator>> The composition of the present invention may contain a thermal radical polymerization initiator insofar as it does not depart from the gist of the present invention. The thermal radical polymerization initiator is a compound which generates a radical by thermal energy and starts or promotes polymerization of a polymerizable compound. By adding a thermal radical polymerization initiator, cyclization of the polyimide precursor can be carried out, and polymerization of the polyimide precursor can be carried out, so that higher heat resistance can be achieved. Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

When the thermal radical polymerization initiator is contained, the content thereof is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass, even more preferably from 5 to 15%, based on the total solid content of the composition of the present invention. quality%. The thermal radical polymerization initiator may be contained alone or in combination of two or more. When two or more kinds of thermal radical polymerization initiators are contained, the above range is preferred.

<<Solvent>> The composition of the present invention preferably contains a solvent. The solvent can be arbitrarily used by a known person. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, anthracenes, and decylamines. Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (for example, methyl alkoxyacetate, alkoxylate) Ethyl acetate, alkoxy butyl acetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.) , 3-alkoxypropionic acid alkyl esters (for example, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate, 3 -ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (for example, 2-alkoxy) Methyl propyl propionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 -propyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)) Methyl 2-alkoxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (for example, methyl 2-methoxy-2-methylpropionate, 2-B Ethyl oxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, Ethyl 2-oxobutanoate or the like. Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, and ethyl cellosolve acetate. Ester, 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 Acid esters, etc. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include toluene, xylene, anisole, limonene, and the like. As a fluorene, for example, dimethyl fluorene is exemplified as a suitable one. Examples of the guanamines include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide. Wait.

The solvent is preferably a mixture of two or more types from the viewpoint of improvement in coating surface shape and the like. Wherein, it is selected from the group consisting of 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 hydrazine, ethyl carbitol acetate, butyl carbitol A mixed solution of two or more of an acid ester, propylene glycol methyl ether and propylene glycol methyl ether acetate is preferred. It is particularly preferable to use both dimethyl hydrazine and γ-butyrolactone.

The content of the solvent is preferably from 5 to 80% by mass based on the total solid content of the composition of the present invention, and the total solid content concentration of the composition of the present invention is The amount of 5 to 70% by mass is more preferably the total solid content concentration of the composition of the present invention is particularly preferably 10 to 60% by mass. The content of the solvent may be adjusted depending on the desired thickness and the coating method. The solvent may be contained alone or in combination of two or more. When two or more solvents are contained, the total range is preferably in the above range.

<<Radical Polymerizable Compound>> The composition of the present invention is preferably a radically polymerizable compound (hereinafter also referred to as "polymerizable monomer"). By adopting such a configuration, a cured film excellent in heat resistance can be formed.

As the polymerizable monomer, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include a group having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth)acryl fluorenyl group, and an allyl group. A radically polymerizable (meth)acrylonitrile group is preferred.

The number of the radical polymerizable groups which the polymerizable monomer may have may be one or two or more. However, it is preferred that the polymerizable monomer has two or more radical polymerizable groups, and three or more of them are more preferable. good. The upper limit is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less.

The molecular weight of the polymerizable monomer is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 900 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.

From the viewpoint of the developability, the composition of the present invention preferably contains at least one polymerizable monomer having two or more functional groups containing two or more polymerizable groups, and more preferably at least one polymerizable monomer having at least one trifunctional or higher functional group. . Further, a mixture of a bifunctional polymerizable monomer and a trifunctional or higher polymerizable monomer may also be used. Further, the number of functional groups of the polymerizable monomer means the number of radical polymerizable groups in one molecule.

Specific examples of the polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof and guanamines. Preferred are esters of unsaturated carboxylic acids with polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. Further, an unsaturated carboxylic acid ester having an affinity substituent such as a hydroxyl group, an amine group or a fluorenyl group, or an addition reaction product of a monofunctional or polyfunctional isocyanate or epoxy group, and a monofunctional group may be suitably used. Or a dehydration condensation reaction of a polyfunctional carboxylic acid or the like. Further, an unsaturated carboxylic acid ester having an electrophilic substituent such as an isocyanate group or an epoxy group or an addition reaction of a guanamine with a monofunctional or polyfunctional alcohol, an amine or a thiol, and a halogen group or a toluene A substituted reactant of an unsaturated carboxylic acid ester or a decylamine having a destructive substituent such as a sulfonyloxy group and a monofunctional or polyfunctional alcohol, an amine or a thiol is also suitable. Further, as another example, in place of the above unsaturated carboxylic acid, a compound group substituted with a vinylbenzene derivative such as an unsaturated phosphonic acid or styrene, a vinyl ether or an allyl ether can be used. As a specific example, the description of paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents are incorporated in the present specification.

Further, a compound having a polymerizable monomer having a boiling point of 100 ° C or higher at normal pressure is also preferred. Examples thereof include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, and pentaerythritol III ( Methyl) acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexane diol (methyl) Acrylate, trimethylolpropane tris(propylene oxypropyl)ether, tris(propylene decyloxyethyl)isocyanate, glycerol or trimethylolethane in polyfunctional alcohols A compound which is (meth) acrylated after addition of ethylene oxide or propylene oxide, Japanese Patent Publication No. Sho 48-41708, Japanese Patent Publication No. Sho-50-6034, and Japanese Patent Laid-Open No. Sho 51-37193 The polyester acrylates described in Japanese Patent Publication No. Sho 49-43191, Japanese Patent Publication No. Sho 49-43191, and Japanese Patent Publication No. Sho 52-30490 , as an epoxy acrylate such as a reaction product of an epoxy resin and (meth)acrylic acid Acrylate or methacrylate, and a mixture of these. Further, a compound described in paragraphs 0254 to 0257 of JP-A-2008-292970 is also suitable. In addition, a polyfunctional (meth)acrylate obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group or an ethylenically unsaturated group such as glycidyl (meth)acrylate can be used. Further, as another preferable polymerizable monomer, an anthracene ring described in Japanese Patent Laid-Open No. 2010-160418, Japanese Patent Laid-Open No. 2010-129825, and No. 4,364,216, and the like, More than one compound containing a group having an ethylenically unsaturated bond or a cardo resin. Further, as another example, a specific unsaturated compound described in JP-A-46-43946, JP-A No. 1-40337, and JP-A No. 1-40336 can be cited. A vinylphosphonic acid-based compound or the like described in Japanese Laid-Open Publication No. 25493. Further, a compound containing a perfluoroalkyl group described in JP-A-61-22048 can also be used. Further, as a photopolymerizable monomer and oligomer, "Journal of the Adhesion Society of Japan" vol. 20, No. 7, and pages 300 to 308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 can be preferably used, and the contents are incorporated in the present specification.

Further, the following compounds described in the formula (1) and the formula (2) together with the specific examples thereof can also be used as a polymerizable monomer, which is added to a polyfunctional alcohol, in the Japanese Patent Publication No. Hei 10-62986. A compound obtained by (meth)acrylation after ethylene oxide or propylene oxide.

Furthermore, the compound described in paragraphs 0104 to 0131 of JP-A-2015-187211 can be used as a polymerizable monomer, and the contents are incorporated in the present specification.

As a polymerizable monomer, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD) D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D- 310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth) acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; Shin-Nakamura Chemical) It is preferred that the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue. It is also possible to use their oligomer type.

As a commercial item of a polymerizable monomer, for example, SR-494, which is a 4-functional acrylate having four ethylene oxide chains, as a bifunctional acrylic acid having four ethyleneoxy chains, can be cited as a product of Sartomer Company, Inc. As a methyl ester of Sartomer Company, Inc., manufactured by SR-209, Nippon Kayaku Co., Ltd., as a 6-functional acrylate having 6 pentylene oxide chains, as DPCA-60 having 3 isomerized butoxy chains Trifunctional acrylate TPA-330, NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (NOF CORPORATION) .)).

As the polymerizable monomer, an amine such as that described in JP-A-H08-41708, JP-A-53-37193, JP-A No. 2-32293, and JP-A No. 2-16765 The urethane acrylates, the epexes described in JP-A-58-49860, JP-A-56-17654, JP-A-62-39417, and JP-A-62-39418 A urethane compound of an ethane-based skeleton is also suitable. In addition, as the polymerizable monomer, an amine group structure in the molecule described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Or a compound of a sulfide structure.

The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group or a phosphoric acid group. Among the polymerizable monomers having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic anhydride to have an acid group polymerization. The sex monomer is better. Particularly preferred is a polymerizable monomer having an acid group in which an unreacted hydroxyl group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride, and an aliphatic polyhydroxy compound is used as neopentyl alcohol and/or dipentaerythritol. Compound. As a commercial item, for example, as a polybasic acid-modified acrylic oligomer manufactured by TOAGOSEI CO., LTD., M-510, M-520, etc. are mentioned. The polymerizable monomer having an acid group may be used singly or in combination of two or more. Further, if necessary, a polymerizable monomer having no acid group and a polymerizable monomer having an acid group can be used at the same time. The acid value of the polymerizable monomer having an acid group is preferably from 0.1 to 40 mgKOH/g, particularly preferably from 5 to 30 mgKOH/g. When the acid value of the polymerizable monomer is within the above range, the production or handling property is excellent, and the developability is excellent. Moreover, the polymerizability is also good.

The content of the polymerizable monomer is preferably from 1 to 50% by mass based on the total solid content of the composition of the present invention from the viewpoint of good polymerizability and heat resistance. The lower limit is preferably 5% by mass or more. The upper limit is preferably 30% by mass or less. The polymerizable monomers may be used singly or in combination of two or more. Further, the mass ratio of the polyimine precursor to the polymerizable monomer (polyimine precursor/polymerizable monomer) is preferably 98/2 to 10/90, and 95/5 to 30/70 is more. Preferably, 90/10 to 50/50 is further preferred. When the mass ratio of the polyimine precursor to the polymerizable monomer is within the above range, a cured film having more excellent polymerizability and heat resistance can be formed.

From the viewpoint of suppressing the warpage controlled by the modulus of elasticity of the cured film, the composition of the present invention can preferably use a monofunctional polymerizable monomer. As the monofunctional polymerizable monomer, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxy group can be preferably used. Ethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxy ethyl (meth) acrylate, N - (meth)acrylic acid derived from -hydroxymethyl (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate N-vinyl compounds such as N-vinylpyrrolidone and N-vinyl caprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate and the like A propyl compound or the like. As the monofunctional polymerizable monomer, in order to suppress volatilization before exposure, a compound having a boiling point of 100 ° C or higher at normal pressure is also preferable.

<<Other Polymerizable Compound>> The composition of the present invention can further contain a polymerizable compound other than the above-described polyimine precursor and radical polymerizable compound. Examples of the other polymerizable compound include a compound having a methylol group, an alkoxymethyl group or a fluorenyloxymethyl group; an epoxy compound; an oxetane compound; and a benzofluorene compound.

(Compound having a methylol group, an alkoxymethyl group or a decyloxymethyl group) As the compound having a methylol group, an alkoxymethyl group or a fluorenyloxymethyl group, a compound represented by the following formula (AM1) is preferred.

[Chemical Formula 45] (wherein t represents an integer of 1 to 20, R ⁴ represents a t-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or An organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.

The content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass based on 100 parts by mass of the polyimine precursor. More preferably, it is 10 to 35 mass parts. In addition, the compound represented by the following formula (AM4) is contained in an amount of 10 to 90% by mass in the total amount of the other polymerizable compound, and a compound represented by the following formula (AM5) is also preferably contained in an amount of 10 to 90% by mass.

[Chemical Formula 46] (wherein R ⁴ represents a divalent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms; R ⁷ represents an organic group having 1 to 10 carbon atoms.)

[Chemical Formula 47] (wherein, u represents an integer of 3 to 8, R ⁴ represents a u-valent organic group having 1 to 200 carbon atoms, R ⁵ represents a group represented by -OR ⁶ or -OCO-R ⁷ , and R ⁶ represents a hydrogen atom. Or an organic group having 1 to 10 carbon atoms, and R ⁷ represents an organic group having 1 to 10 carbon atoms.)

When the composition of the present invention is applied to a concave-convex substrate by using the compound having a methylol group or the like, the occurrence of cracks can be more effectively suppressed. In addition, it is excellent in pattern workability, and the temperature at which the mass is reduced by 5% is 350° C. or higher, and more preferably a cured film having a high heat resistance of 380° C. or higher. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (above, trade name, manufactured by ASAHI YUKIZAI CORPORATION), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC MX -290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethoxymethyl-4-t-buthylphenol (2,6-dimethoxymethyl-4-t-butylphenol), 2, 6-dimethoxymethyl-p-cresol (2,6-dimethoxymethyl-p-cresol), 2,6-diacethoxymethyl-p-cresol (2,6-2-diethoxymethyl-methyl) Phenol) and the like.

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

(Epoxy compound (compound having an epoxy group)) As the epoxy compound, a compound having two or more epoxy groups in one molecule is preferred. The epoxy is subjected to a crosslinking reaction based on 200 ° C or less, and it is difficult to cause film shrinkage because it does not cause a dehydration reaction derived from crosslinking. Therefore, by containing an epoxy compound, low-temperature hardening and warpage of the composition can be effectively suppressed.

The epoxy compound preferably contains a polyethylene oxide group. Thereby, the modulus of elasticity is further lowered, and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of the epoxy compound include an extended alkyl diol type epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a propylene glycol diglycidyl ether, and a polypropylene glycol diglycidyl ether. The epoxy group-containing epoxy resin such as an alkyl glycol type epoxy resin or polymethyl (glycidoxypropyl) alkane is not limited thereto. Specifically, EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700 EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) ) EXA-4850-150, EPICLON EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822 (above, trade name, manufactured by DIC Corporation), RIKARESIN (registered trademark) BEO-60E (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S (above, trade name, manufactured by ADEKA CORPORATION). Among these, an epoxy resin containing a polyethylene oxide group is preferable from the viewpoint of suppressing warpage and excellent heat resistance. For example, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4822, and RIKARESIN (registered trademark) BEO-60E contain a polyethylene oxide group, and therefore are preferable.

The content of the epoxy compound is preferably 5 to 50 parts by mass based on 100 parts by mass of the polyimide precursor, more preferably 10 to 50 parts by mass, still more preferably 10 to 40 parts by mass. When the content of the epoxy compound is 5 parts by mass or more, the warpage of the obtained cured film can be suppressed, and if it is 50 parts by mass or less, pattern embedding due to reflow at the time of hardening can be further suppressed.

(Oxetane compound (compound having oxetanyl group)) The oxetane compound can be exemplified by a compound having two or more oxetane rings in one molecule, 3-ethyl 3-hydroxymethoxyoxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 3-ethyl-3-(2 -ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester, and the like. As a specific example, the ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, and OXT-223) manufactured by TOAGOSEI CO., LTD. can be suitably used, and these may be used alone or in combination. More than one species.

The content of the oxetane compound is preferably 5 to 50 parts by mass based on 100 parts by mass of the polyimide precursor, more preferably 10 to 50 parts by mass, still more preferably 10 to 40 parts by mass.

(Benzoindole compound (compound having a benzoxazolyl group)) The benzofluorene compound does not generate degassing upon hardening due to a crosslinking reaction derived from a ring-opening addition reaction, thereby reducing heat shrinkage and suppressing generation. Warpage is therefore preferred.

Preferable examples of the benzofluorene compound include Ba type benzopyrene, Bm type benzopyrene (the above-mentioned trade name, manufactured by Shikoku Chemicals Corporation), and benzopyrene of polyhydroxystyrene resin. A product, a novolac type dihydrobenzopyrene compound. These may be used alone or in combination of two or more.

The content of the benzofluorene compound is preferably 5 to 50 parts by mass based on 100 parts by mass of the polyimide precursor, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass.

<<Migration inhibitor>> The photosensitive resin composition further preferably contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress transfer of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer. The migration inhibitor is not particularly limited, and examples thereof include a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole). a compound of a ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, a 6H-pyran ring, a triazine ring), having a thiourea A compound, a hindered phenol compound, a salicylic acid derivative compound, and an anthracene derivative compound. In particular, a triazole compound such as triazole or benzotriazole, a tetrazole compound such as tetrazole or benzotetrazole can be preferably used.

Further, an ion trapping agent that traps an anion such as a halogen ion can also be used.

As the other migration inhibitor, the rust inhibitor described in paragraph 0094 of JP-A-2013-15701, and the compound described in paragraphs 0073 to 0076 of JP-A-2009-283711 can be used. A compound described in paragraph 0052 of JP-A-59656, and a compound described in paragraphs 0114, 0116, and 0118 of JP-A-2012-194520.

Specific examples of the migration inhibitor include the following compounds. [Chemical Formula 48]

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

<<Polymerization inhibitor>> The composition of the present invention preferably contains a polymerization inhibitor. As the polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butyl catechol, p-benzene can be suitably used. Bismuth, diphenyl-p-benzoquinone, 4,4' thiobis(3-methyl-6-tert-butylphenol), 2,2' methylenebis(4-methyl-6-third Butylphenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2 - cyclohexanediaminetetraacetic acid, glycol ether diamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitrogen 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl-N-sulfopropylamine)phenol, N-nitroso-N- (1-Naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-t-butyl)phenylmethane or the like. 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 WO2015/125469 can also be used. Further, the following compound (Me is a methyl group) can also be used. [Chemical Formula 49] When the composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably from 0.01 to 5% by mass based on the total solid content of the composition of the present invention. The polymerization inhibitor may be used alone or in combination of two or more. When the polymerization inhibitor is two or more kinds, the total range is preferably in the above range.

<<Metal Adhesive Improver>> The composition of the present invention preferably contains a metal adhesion improver for improving the adhesion to a metal material such as an electrode or a wiring. The metal adhesion improving agent may, for example, be a decane coupling agent.

Examples of the decane coupling agent include the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, and the compounds described in paragraphs 0063 to 0071 of International Publication WO2011/080992A1, and JP-A-2014. A compound described in paragraphs 0060 to 0061 of JP-A No. 191252, a compound described in paragraphs 0045 to 0052 of JP-A-2014-41264, and a compound described in paragraph 0055 of International Publication WO2014/097594. Further, it is also preferred to use two or more different decane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferred to use the following compounds as the decane coupling agent. In the following formula, Et represents an ethyl group. [Chemical Formula 50]

In addition, the metal-adhesive improver can also use the compound described in paragraphs 0046 to 0049 of JP-A-2014-186186, and the sulfides described in paragraphs 0032 to 0043 of JP-A-2013-072935.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the polyimide intermediate. When the amount is 0.1 part by mass or more, the adhesion between the cured film and the metal layer after the curing process is improved, and the heat resistance and mechanical properties of the cured film after the curing process are improved by 30 parts by mass or less. The metal adhesion improver may be used alone or in combination of two or more. When two or more types are used, it is preferable that they are in the above range.

<<Base generator>> The composition used in the present invention may contain a base generator. The alkali generating agent may be a hot base generating agent or a photobase generating agent, and at least a photobase generating agent is preferred.

<<<Thermal base generator>>> The type of the hot base generator is not particularly limited, and includes an acidic compound containing a base selected from the group consisting of heating to 40 ° C or higher and an anion and ammonium cation having a pKa1 of 0 to 4. A hot base generator of at least one of the ammonium salts is preferred. Wherein, pKa1 represents a logarithmic marker (-Log ₁₀ Ka) of the dissociation constant (Ka) of the first proton of the polybasic acid. By compounding such a compound, the cyclization reaction of the polyimide precursor can be carried out at a low temperature, and a composition having more excellent stability can be formed. Further, since the hot base generator does not generate an alkali without heating, even if it is coexisted with the polyimide precursor, cyclization of the polyimide precursor during storage can be suppressed, and the storage stability is excellent.

The thermal base generator in the present invention contains at least one selected from the group consisting of an acidic compound (A1) which generates a base upon heating to 40 ° C or higher, and an ammonium salt (A2) having an anion of an anion of pKa1 of 0 to 4 and an ammonium cation. Since the acidic compound (A1) and the ammonium salt (A2) generate a base upon heating, the cyclization reaction of the polyimide precursor can be promoted by the base derived from the compounds, and the polymerization can be carried out at a low temperature. Cyclization of the quinone imine precursor. Further, even if these compounds coexist with the polyimine precursor which is cyclized and hardened by alkali, the cyclization of the polyimide precursor is hardly carried out without heating, so that excellent aggregation can be stably produced. Imine precursor composition. Further, in the present specification, the acidic compound means that 1 g of the compound is collected in a container, and a mixture of 50 ml of ion-exchanged water and tetrahydrofuran (mass ratio of water / tetrahydrofuran = 1/4) is added, and the mixture is stirred at room temperature for 1 hour. The solution was measured to have a value of less than 7 at 20 ° C using a pH meter.

In the present invention, the alkali generating temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C or lower, more preferably 180 ° C or lower, and further preferably 165 ° C or lower. The lower limit of the base generation temperature is preferably 130 ° C or more, more preferably 135 ° C or more. When the alkali production temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C or more, the alkali is less likely to be generated during storage, and therefore, an excellent polyimide intermediate precursor composition can be stably produced. When the base production temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C or lower, the cyclization temperature of the polyimide precursor can be lowered. Regarding the alkali generation temperature, for example, by differential scanning calorimetry, the compound is heated to 250 ° C at 5 ° C / min in a pressure resistant capsule, the peak temperature of the exothermic peak having the lowest temperature is read, and the peak temperature is taken as the alkali generation temperature. And the measurement can be performed.

In the present invention, the base-based second amine or the third amine produced by the hot base generator is preferred, and the third amine is more preferred. Since the third amine has a high basicity, the cyclization temperature of the polyimide precursor can be further lowered. Further, the alkalinity of the base produced by the hot alkali generating agent is preferably 80 ° C or more, more preferably 100 ° C or more, and still more preferably 140 ° C or more. Further, the molecular weight of the base to be produced is preferably from 80 to 2,000. The lower limit is preferably 100 or more. The upper limit is preferably 500 or less. Further, the value of the molecular weight is a theoretical value obtained from the structural formula.

In the present invention, the acidic compound (A1) is preferably one or more selected from the group consisting of an ammonium salt and a compound represented by the formula (101) or (102) which will be described later.

In the present invention, the above ammonium salt (A2) is preferably an acidic compound. Further, the above ammonium salt (A2) may be a compound containing an acidic compound which generates a base upon heating to 40 ° C or higher (preferably 120 to 200 ° C), or may be heated to 40 ° C or higher (preferably 120 to 200). At ° C), a compound other than the acidic compound of the base is produced.

<<<<Ammonium Salt>>>> In the present invention, the ammonium salt refers to a salt of an ammonium cation and an anion represented by the following formula (101) or formula (102). The anion may be bonded to any part of the ammonium cation via a covalent bond or may be present outside the molecule of the ammonium cation, but is preferably outside the molecule of the ammonium cation. Further, the fact that the anion is outside the molecule of the ammonium cation means that the ammonium cation and the anion are not bonded via a covalent bond. Hereinafter, the extra-molecular anion of the cation portion is also referred to as a counter anion. Formula (101) Formula (102) [Chemical Formula 51] In the formula, R ¹ to R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, and R ⁷ represents a hydrocarbon group. R ¹ and R ² , R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁵ and R ⁷ may be bonded to each other to form a ring.

The ammonium cation is preferably represented by any one of the following formulae (Y1-1) to (Y1-5). [Chemical Formula 52]

In the formulae (Y1-1) to (Y1-5), R ¹⁰¹ represents an n-valent organic group, and R ¹ and R ^{7 have the} same meanings as R ¹ and R ⁷ in the formula (101) or the formula (102). In the formulae (Y1-1) to (Y1-4), Ar ¹⁰¹ and Ar ¹⁰² each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5.

In the present embodiment, the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation. The upper limit of the pKa1 of the anion is preferably 3.5 or less, and more preferably 3.2 or less. The lower limit is preferably 0.5 or more, more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the heterocyclic-containing polymer precursor can be cyclized at a lower temperature, and the stability of the composition can be improved. When pKa1 is 4 or less, the stability of the thermal base generator is good, and the generation of alkali can be suppressed without heating, and the stability of the composition is good. When pKa1 is 0 or more, the produced alkali is not easily neutralized, and the cyclization efficiency of the heterocyclic-containing polymer precursor or the like is good. The type of the anion is preferably one selected from the group consisting of a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and the carboxylate anion is more preferable from the viewpoint of the stability of the salt and the thermal decomposition property. That is, a salt of an ammonium salt-based ammonium cation and a carboxylate anion is more preferable. The carboxylate anion is preferably an anion having a carboxylic acid having two or more valences of two or more carboxyl groups, more preferably an anion of a divalent carboxylic acid. In this case, a hot alkali generating agent capable of further improving the stability, curability, and developability of the composition can be used. In particular, by using an anion of a divalent carboxylic acid, the stability, hardenability, and developability of the composition can be further improved. In the present embodiment, an anion of a carboxylic acid having a carboxylate anion such as pKa1 of 4 or less is preferred. The pKa1 is preferably 3.5 or less, and more preferably 3.2 or less. In this way, the stability of the composition can be further improved. Wherein, and pKa1 representation into a number of isolated reciprocal constant of the first proton acid, and can refer to a physical identification method (Determination of Organic Structures by Physical Methods) the organic structure (OF: Brown, HC, McDaniel, DH, Hafliger, O. , Nachod, FC; editor: Braude, EA, Nachod, FC; US academic publishing house (academic Press, New York), 1955), or for information on biochemical studies (data for biochemical Research) (author: Dawson, RMCet al ; Oxford, Oxford, Clarendon Press, 1959). For the compounds described in these documents, the values calculated by the structural formula using software of ACD/pKa (manufactured by ACD/Labs) are used.

The carboxylate anion is preferably represented by the following formula (X1). [Chemical Formula 53] In the formula (X1), EWG represents an electron withdrawing group.

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

The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6). [Chemical Formula 54] In the formulae (EWG-1) to (EWG-6), R ^x1 to R ^x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group.

In the present embodiment, the carboxylate anion is preferably represented by the following formula (XA). Formula (XA) [Chemical Formula 55] In the formula (XA), L ¹⁰ represents a single bond or a divalent linking group selected from an alkyl group, an alkenyl group, an aromatic group, -NR ^X - and a combination thereof, and R ^X represents a hydrogen atom, an alkyl group, Alkenyl or aryl.

Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetate anion, and an oxalate anion. The details of the hot base generator can be described in paragraphs 0021 to 0077 of JP-A-2016-027357, and these contents are incorporated in the present specification. As the thermal base generator, the following compounds are exemplified. [Chemical Formula 56] [Chemical Formula 57]

[Chemical Formula 58] [Chemical Formula 59]

When a hot base generator is used, the content of the hot base generator in the composition is preferably from 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less. The hot base generator can be used alone or in combination of two or more. When two or more types are used, it is preferred that the total amount is the above range.

<<<Photobase generator>>> The photosensitive resin composition used in the present invention may contain a photobase generator. The photobase generator is a substance which generates an alkali by exposure, and does not exhibit activity under normal conditions of normal temperature and normal pressure. However, when electromagnetic waves are irradiated and heated as an external stimulus, an alkali (basic substance) is generated. There is no particular limitation on the person. The base produced by the exposure functions as a catalyst for curing the polyimide precursor by heating, and therefore can be suitably used in a negative type.

In the present invention, a known one can be used as the photobase generator. For example, such as M. Shirai, and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Kakuoka Masahiro, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev ., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol , 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S. Yoshitaka, J. Photopolym. Sci. Technol , 9, 13, (1996); K. Suyama, H. Araki, M. Shirai, J. Photopolym. Sci. Technol., 19, 81 (2006), which can be cited as a transition metal compound complex, having An ionic compound, a carbamate derivative, an oxime ester derivative, or a hydrazine neutralized by a structure such as an ammonium salt, such as a salt formed by a hydrazine moiety and a carboxylic acid, which is formed by a salt component by a latent component. A nonionic compound in which an alkali component is latent by a urethane bond or a hydrazone bond or the like.

The basic substance produced by the photobase generator is not particularly limited, and examples thereof include a compound having an amine group, particularly a polyamine such as a monoamine or a diamine, or hydrazine. The resulting basic substance is preferably a compound having a more basic amino group. The reason for this is that the catalytic action such as the dehydration condensation reaction in the ruthenium imidization of the polyimide precursor is strong, and the addition of a smaller amount enables the dehydration condensation reaction to be exhibited at a lower temperature. Catalytic effect. That is, since the catalytic effect of the generated alkaline substance is large, the apparent sensitivity as a negative photosensitive resin composition is improved. From the viewpoint of the above catalyst effect, hydrazine and an aliphatic amine are preferred. As the photobase generator used in the present invention, a compound containing an aromatic ring and having a basic substance having an amine group is preferred.

The photobase generator according to the present invention may, for example, be a photobase generator having a cinnamate cinnamate structure as disclosed in Japanese Laid-Open Patent Publication No. 2009-80452 and International Publication No. 2009/123122. A photobase generator having a urethane structure as disclosed in JP-A-2008-247747, and JP-A-2007-249013, and JP-A-2008-003581 Although a photobase generator having an anthracene structure or an aminoformamidine structure is disclosed as described above, the present invention is not limited thereto, and a known photobase generator can be used.

In addition, examples of the photobase generator include the compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of JP-A-2012-93746, and paragraphs 0022 to 0069 of JP-A-2013-194205. The compound described in paragraphs 0026 to 0074 of JP-A-2013-204019, and the compound described in paragraph 0052 of WO2010/064631.

As a commercial product of a photobase generator, WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB can also be used. -172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.). Further, as the photobase generator, the following compounds are exemplified. [Chemical Formula 60]

When a photobase generator is used, the content of the photobase generator in the composition is preferably from 0.1 to 50% by mass based on the total solid content of the composition. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, more preferably 20% by mass or less. The photobase generator can be used alone or in combination of two or more. When two or more types are used, the above range is preferable.

<<Other Additives>> The composition of the present invention can be used for various additives such as a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, and an advanced one, as long as the effects of the present invention are not impaired. The fatty acid derivative, the inorganic particles, the curing agent, the curing catalyst, the filler, the antioxidant, the ultraviolet absorber, the aggregation inhibitor, and the like are blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

<<<Thermal acid generator>>> The composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating and promotes cyclization of the polyimide precursor to further improve the mechanical properties of the cured film. Examples of the thermal acid generator include the compounds described in paragraph 0059 of JP-A-2013-167742.

The content of the thermal acid generator is preferably 0.01 parts by mass or more based on 100 parts by mass of the polyimide precursor, and more preferably 0.1 part by mass or more. When the thermal acid generator is contained in an amount of 0.01 parts by mass or more, the crosslinking reaction and the cyclization of the polyimide precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. In addition, the content of the thermal acid 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 insulating properties of the cured film. The thermal acid generator may be used singly or in combination of two or more. When two or more types are used, it is preferred that the total amount becomes the above range.

<<<Sensitivity Pigment>>> The composition of the present invention may contain a sensitizing dye. The sensitizing dye absorbs specific active radiation and becomes an electronically excited state. The sensitizing dye which is in an electronically excited state is brought into contact with a hot alkali generating agent, a thermal radical polymerization initiator, a radical polymerization initiator, and the like to cause electron transfer, energy transfer, heat generation and the like. Thereby, the thermal base generator, the thermal radical polymerization initiator, and the radical polymerization initiator are chemically changed to be decomposed, and a radical, an acid or a base is generated. For the details of the sensitizing dye, the descriptions of paragraphs 0161 to 0163 of JP-A-2016-027357 can be referred to, and the contents are incorporated in the present specification.

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

<<<Chain Transfer Agent>> The composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in the third edition of the Polymer Dictionary (The Society of Polymer Science, Japan, 2005) 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, or GeH in the molecule is used. These may be generated by supplying hydrogen to a low-activity radical to generate a radical, or by oxidizing, by generating a radical by deprotonation. In particular, a thiol compound can be preferably used (for example, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 3-mercaptotriazole, 5-mercaptotetrazole, 5-mercaptotetrazole Class, etc.).

When the composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the total solid content of the composition of the present invention. It is particularly preferably 1 to 5 parts by mass. The chain transfer agent may be used alone or in combination of two or more. When the chain transfer agent is two or more, the total range is preferably in the above range.

<<<Interacting Agent>>> From the viewpoint of further improving the coatability, various surfactants can be added to the composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a lanthanoid surfactant can be used. Further, the following surfactants are also preferred. [Chemical Formula 61]

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

<<<High-Fatty Fatty Acid Derivative>> In order to prevent polymerization inhibition by oxygen, a higher fatty acid derivative such as behenic acid or behenyl glutamine may be added to the composition of the present invention after coating. The drying process is biased by the surface of the composition. When the composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably from 0.1 to 10% by mass based on the total solid content of the composition of the present invention. The higher fatty acid derivatives may be used alone or in combination of two or more. When the higher fatty acid derivatives are two or more, the total range is preferably in the above range.

<<Restriction of Other Containing Substances>> From the viewpoint of coating the surface, the composition of the present invention preferably has a moisture content of less than 5% by mass, more preferably less than 1% by mass, and more preferably less than 0.6% by mass. .

From the viewpoint of the insulating property, the metal content of the composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and particularly preferably less than 0.5 ppm by mass. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When a plurality of metals are contained, the total of the metals is preferably in the above range. In addition, as a method of reducing the metal impurities which are inadvertently contained in the composition of the present invention, a raw material having a small metal content is selected as a raw material constituting the composition of the present invention, and the raw materials constituting the composition of the present invention are filtered. The apparatus was filtered, and the inside of the apparatus was lined with polytetrafluoroethylene to carry out distillation under conditions where contamination was suppressed as much as possible.

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

A conventionally known storage container can be used as the storage container of the composition of the present invention. In addition, as a storage container, it is preferable to use a multi-layer bottle in which the inner wall of the container is composed of six kinds of six layers of resin, and a bottle having six layers of resin in a seven-layer structure for the purpose of suppressing the incorporation of impurities into the material or the composition. As such a container, for example, a container described in JP-A-2015-123351 can be cited.

<<Preparation of Composition>> The composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be carried out by a conventionally known method. Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign matter such as garbage or fine particles in the composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter can be pre-cleaned with an organic solvent. In the filtration process of the filter, a plurality of filters can be used in parallel or in series. When a plurality of filters are used, a filter having a different aperture and/or material can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, it is possible to filter by circulation. Also, filtration can be carried out after pressurization. When the filtration is carried out after the pressurization, the pressure for pressurization is preferably 0.05 MPa or more and 0.3 MPa or less. In addition to the filtration using a filter, an impurity removal treatment using an adsorbent material can also be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent material. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as tannin or zeolite, or an organic adsorbent such as activated carbon can be cited.

<Curing film, semiconductor device, method for producing cured film, method for producing laminated body, and method for producing semiconductor device> Next, the cured film, semiconductor device, method for producing cured film, method for producing laminated body, and semiconductor device of the present invention The manufacturing method will be described. The cured film of the present invention is obtained by hardening the 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. In addition, the upper limit 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 as a laminate. A seed layer system having two or more layers of the cured film of the present invention preferably has a metal layer between the cured films. Such a metal layer can be preferably used as a metal wiring such as a rewiring layer.

The field of the cured film of the present invention is exemplified by an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, and the like. In particular, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device. Further, the cured film of the present invention can also be used for an electron photoresist, a galvanic resist, an etching resist, a solder top resist, or the like. Further, the cured film of the present invention can also be used for the production of a layout such as an offset printing plate or a screen printing surface, use of a molded member, electrons, particularly a protective paint for a microelectronic, and production of a dielectric layer.

The method for producing a cured film of the present invention includes the case of using the composition of the present invention. Preferably, the method for producing a cured film comprising a photosensitive resin composition layer forming process, applying the photosensitive resin composition of the present invention to a substrate to form a layer, and an exposure process for the above-mentioned photosensitivity The resin composition layer is subjected to exposure; and a development treatment process is performed to develop the exposed photosensitive resin composition layer (resin layer). The photosensitive resin composition of the present invention can be preferably used in the case of performing negative development.

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 layered product of the present invention, in the method for producing a cured film of the present invention, after the cured film is formed, the photosensitive resin composition layer forming process, the exposure process, and the development process are preferably performed in order. In particular, it is preferable that the photosensitive resin composition layer forming process, the exposure process, and the development process are sequentially performed 2 to 5 times (that is, 3 to 6 times in total). By laminating the cured film in this manner, it is possible to form a laminated body. In the present invention, in particular, after the cured film is provided for development, it is preferred to provide a metal layer in the portion which has been removed by development. The details of this will be described below.

<<Photosensitive Resin Composition Layer Forming Process>> The method for producing a laminate of the present invention includes a process for forming a photosensitive resin composition layer, and applying the photosensitive resin composition to a substrate to form a layer. The type of the substrate can be appropriately set depending on the application, but is not particularly limited, and examples thereof include a semiconductor-made substrate such as tantalum, tantalum nitride, polycrystalline germanium, cerium oxide, or amorphous germanium, quartz, glass, an optical film, a ceramic material, and a vapor deposited film. A magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, or Fe, paper, an SOG (Spin On Glass), a TFT (Thin Film Transistor) array substrate, an electrode plate of a plasma display panel (PDP), or the like. In the present invention, in particular, a semiconductor-made substrate is preferable, and a germanium substrate is more preferable. Further, when a 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. As a method of applying a photosensitive resin composition to a substrate, coating is preferred. Specifically, examples of the application method include dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, and spin coating method. , slit coating method, inkjet method, and the like. From the viewpoint of 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. The resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration or coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the substrate. However, in the case of a circular substrate such as a wafer, a spin coating method, a spray coating method, an inkjet method, or the like is preferable, and if it is a rectangular substrate, the slit coating is applied. A cloth method, a spray method, an ink jet method, or the like is preferred. 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 method for producing a layered body of the present invention may further include a process of drying after removing the solvent after forming the photosensitive resin composition layer. The preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, and further 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 method for producing a layered body of the present invention includes an exposure process for exposing the photosensitive resin composition layer. The exposure amount is not particularly limited as long as it can cure the photosensitive resin composition. For example, it is preferably 100 to 10000 mJ/cm ² in terms of exposure energy at a wavelength of 365 nm, and more preferably 200 to 8000 mJ/cm ² . The exposure wavelength can be appropriately set in the range of 190 to 1000 nm, and 240 to 550 nm is preferable.

<<Developing Process>> The method for producing a layered body of the present invention includes a development process for performing a negative development process on the exposed photosensitive resin composition layer. The unexposed portion (non-exposed portion) is removed by performing negative development. The development method is not particularly limited as long as a desired pattern can be formed. For example, a development method such as spin coating, spraying, dipping, or ultrasonic can be employed. Development is carried out using a developing solution. The developer can be used without any particular limitation as long as the unexposed portion (non-exposed portion) can be removed. It is preferred that the developer contains an organic solvent. As the organic solvent, examples of the ester include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and ethyl butyrate. Ester, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetate (eg methyl alkoxyacetate, Ethyl alkoxyacetate, butyl alkoxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate) Et.), 3-alkoxypropionic acid alkyl esters (eg, methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (for example, methyl 3-methoxypropionate) , 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.), 2-alkoxypropionic acid alkyl esters (Example: 2- Methyl alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate) Methyl 2-alkoxy-2-methylpropanoate and ethyl 2-alkoxy-2-methylpropanoate (for example, methyl 2-methoxy-2-methylpropionate, 2- Ethyl ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, methyl 2-oxobutanoate, Ethyl 2-oxobutanoate or the like, and as the ether, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetic acid can be suitably used. Ester, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, and the like, and as the ketone, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl are suitably exemplified. Examples of the aromatic hydrocarbons include, for example, toluene, xylene, anisole, limonene, and the like, and examples of the anthracene include dimethyl hydrazine. In the present invention, especially cyclopentanone or γ-butyrolactone is preferred, and cyclopentanone is more preferred.

As the development time, 10 seconds to 5 minutes is preferable. The temperature at the time of development is not particularly limited, and it can usually be carried out at 20 to 40 °C. After the treatment with the developer, it is also possible to carry out the rinsing. It is preferred to carry out the rinsing with a solvent different from the developer. For example, rinsing can be performed using a solvent contained in the photosensitive resin composition. The rinsing time is preferably from 5 seconds to 1 minute.

<<Heating Process>> The manufacturing method of the laminated body of the present invention includes a heating process preferably. In the heating process, a cyclization reaction of the polyimide precursor is carried out. In addition, when the composition of the present invention contains a radically polymerizable compound, curing of the unreacted radical polymerizable compound or the like is also performed. The heating temperature (the highest heating temperature) is preferably 50 to 450 ° C, more preferably 140 to 400 ° C, and still more preferably 160 to 350 ° C. The heating is preferably carried out at a temperature elevation rate of from 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 still more preferably 3 to 10 ° C / min. By setting the temperature increase rate to 2° C./min or more, the productivity can be ensured while preventing excessive evaporation of the amine, and by setting the temperature increase rate to 12° C./min or less, the residual stress of the cured film can be alleviated. The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further 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 highest heating temperature is started. For example, when the photosensitive resin composition is applied to a substrate and then dried, the temperature after drying is gradually increased from the boiling point of the solvent contained in the photosensitive resin composition (30 to 200 ° C). It is better. The heating time (heating time at the highest heating temperature) is preferably from 10 to 360 minutes, further preferably from 20 to 300 minutes, and particularly preferably from 30 to 240 minutes. In particular, when a multilayered laminate is formed, heating is preferably carried out at a heating temperature of from 180 ° C to 320 ° C from the viewpoint of adhesion between the layers of the cured film, and heating at 180 ° C to 260 ° C is more preferable. Although the reason is not certain, it is considered that the reason is that the ethynyl group of the polyimide precursor of the interlayer is cross-linked with each other by the temperature.

Heating can be carried out in stages. As an example, the pretreatment process may be carried out, that is, the temperature is raised at 3 ° C / min up to 25 ° C to 180 ° C, and left at 180 ° C for 60 minutes, and then raised at 180 ° C to 200 ° C at 2 ° C / min. Leave at °C for 120 minutes. The heating temperature of the pretreatment process is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and still more preferably 120 to 185 ° C. In the pretreatment process, it is also preferred to carry out the treatment while irradiating ultraviolet rays as described in U.S. Patent No. 9159547. The characteristics of the film can be improved by this pretreatment process. The pretreatment process can be carried out in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be a two-stage or more step, for example, the pretreatment process 1 may be carried out in the range of 100 to 150 ° C, and then the pretreatment process 2 may be carried out in the range of 150 to 200 ° C. Further, it is possible to perform cooling after heating, and as the cooling rate in this case, it is preferably 1 to 5 ° C / min.

The heating process is preferably carried out in a low oxygen concentration environment by preventing the decomposition of the polyimide precursor or the like by flowing an inert gas such as nitrogen, helium or argon. 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 method for producing a layered body of the present invention preferably includes a metal layer forming process for forming a metal layer on the surface of the photosensitive resin composition layer after the development process. The metal layer is not particularly limited, and conventional metal species can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, and copper and aluminum are more preferable, and copper is more preferable. The method of forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the method 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, peeling, electrolytic plating, electroless plating, etching, printing, and a combination of these may be considered. More specifically, a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined are exemplified. The thickness of the metal layer is preferably 0.1 to 50 μm in the thickest thickness portion, and more preferably 1 to 10 μm.

<<Laminating Process>> The manufacturing method of the present invention further includes a lamination process which is preferable. The lamination process includes a series of processes in which the photosensitive resin composition layer forming process, the exposure process, and the development process described above are sequentially performed. Of course, the lamination process may also include the above drying process or heating process. When the build-up process is further performed after the build-up process, the surface activation process may be performed after the above exposure process or after the above-described metal layer formation process. As the surface activation treatment, a plasma treatment is exemplified. It is preferable to carry out the above-mentioned lamination process 2 to 5 times, and it is more preferable to carry out 3 to 5 times. For example, a resin layer such as a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferably three or more layers and seven or less layers, and more preferably three or more layers and five or less layers. That is, in the present invention, in particular, after the metal layer is provided, the photosensitive resin composition layer forming process, the exposure process, and the development process are sequentially performed so as to cover the metal layer. By alternately performing the lamination process of the laminated photosensitive resin composition layer (resin) and the metal layer forming process, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

A semiconductor device including the cured film or laminate of the present invention is also disclosed in the present invention. An embodiment of a semiconductor device in which the composition of the present invention is used in the formation of 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 wafers) 101a to 101d are laminated is disposed on the wiring substrate 120. In the embodiment, the number of layers of the semiconductor element (semiconductor wafer) is mainly four, but the number of layers of the semiconductor element (semiconductor wafer) is not particularly limited, and for example, it may be two or eight layers. 16 layers, 32 layers, etc. Also, it can be one layer.

Each of the plurality of semiconductor elements 101a to 101d includes a semiconductor wafer such as a germanium 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 on the through electrodes are provided on both surfaces of the semiconductor elements.

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

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

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

Hereinafter, the present invention will be described in further detail by way of examples. The materials, the amounts, the ratios, the processing contents, and the processing steps shown in the following examples are equivalent to the scope of the invention, and can be appropriately changed. Therefore, the scope of the present invention is not limited to the specific examples shown below. “Parts” and “%” are quality standards unless otherwise specified.

(Synthesis Example 1) [From 4,4'-oxydiphthalic dianhydride, 4,4'-oxydiphenylamine (4,4'-diaminodiphenyl ether), N-(3'- Polyacetylene precursor of ethynylphenyl)-3,5-diaminobenzamide (compound (1)-1) and 2-hydroxyethyl methacrylate (A-1: radical polymerization) Synthesis of a poly-imine precursor of a base] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 Mixing 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 10.7 g pyridine and 140 g diglyme (diethylene glycol dimethyl ether), stirring at 60 ° C A diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced over 18 hours. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 9.403 g (46.96 mmol) of 4,4'-oxydiphenylamine and 2.950 g (11.74 mmol) of N-(3'-ethynylphenyl)-3,5-diaminobenzimidamide A solution of the amine dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23 ° C for 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 Torr. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor was filtered and removed, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure to obtain a polyimine precursor (A-1). As a result of GPC measurement of the polyimine precursor (A-1), the weight average molecular weight (Mw) was 25,000 as a value in terms of polystyrene. The molar ratio of the repeating unit described below (repeating unit on the left side: repeating unit on the right side) is 80:20. [Chemical Formula 62]

Further, the weight average molecular weight (Mw) is a polystyrene equivalent value in terms of gel permeation chromatography (GPC measurement). HLC-8220 (manufactured by TOSOH CORPORATION) was used as a column using a protective column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION), and the eluent was THF (manufactured by TOSOH CORPORATION). Tetrahydrofuran) was measured. Further, a detector using a UV line (ultraviolet) wavelength of 254 nm was used.

(Synthesis Example 2) [from pyromellitic dianhydride, 4,4'-oxydiphenylamine, N-(3'-ethynylphenyl)-3,5-diaminobenzimidamide (compound ( 1)-1) and polyethylenimine precursor of 2-hydroxyethyl methacrylate (A-2: polyethylenimine precursor having a radical polymerizable group)] 14.06 g (64.5 mmol) Ear) pyromellitic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 10.7 g pyridine and 140 g NMP (N -Methyl-2-pyrrolidone) was mixed and stirred at a temperature of 60 ° C for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 9.403 g (46.96 mmol) of 4,4'-oxydiphenylamine and 2.950 g (11.74 mmol) of N-(3'-ethynylphenyl)-3,5-diaminobenzimidamide A solution of the amine dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23 ° C for 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 Torr. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor was filtered and removed, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure to obtain a polyimine precursor (A-2). As a result of GPC measurement of the polyimine precursor (A-2), the weight average molecular weight (Mw) was 20,000 as a value in terms of polystyrene. The molar ratio of the repeating unit described below (repeating unit on the left side: repeating unit on the right side) is 80:20. [Chemical Formula 63]

(Synthesis Example 3) [From 4,4'-oxydiphthalic dianhydride, p-phenylenediamine, N-(3'-ethynylphenyl)-3,5-diaminobenzamide (Synthesis of Compound (1)-1) and Polyethylenimine Precursor of 2-Hydroxyethyl Methacrylate (A-3: Polyethylenimine Precursor with Radical Polymerizable Group)] 20.0 g ( 64.5 millimoles of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of p-benzoic acid Diphenol, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at 60 ° C for 18 hours to produce 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Diester. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 5.078 g (46.96 mmol) of p-phenylenediamine and 2.950 g (11.74 mmol) of N-(3'-ethynylphenyl)-3,5-diaminobenzimidamide were dissolved in 100 ml. A solution of N-methylpyrrolidone was added to the reaction mixture at 20 to 23 ° C for 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 Torr. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor was filtered and removed, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure to obtain a polyimine precursor (A-3). As a result of GPC measurement of the polyimine precursor (A-3), the weight average molecular weight (Mw) was 20,000 as a value in terms of polystyrene. The molar ratio of the repeating unit described below (repeating unit on the left side: repeating unit on the right side) is 80:20. [Chemical Formula 64]

(Synthesis Example 4) [from 4,4'-oxydiphthalic dianhydride, N-(3'-ethynylphenyl)-3,5-diaminobenzimidamide (compound (1)- 1) Synthesis of polyethylenimine precursor of 2-hydroxyethyl methacrylate (A-4: Polyethylenimine precursor having radical polymerizable group)] 20.0 g (64.5 mmol) 4 4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine The mixture was mixed with 140 g of diglyme and stirred at a temperature of 60 ° C for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, 14.750 g (58.70 mmol) of N-(3'-ethynylphenyl)-3,5-diaminobenzimidamide was dissolved in 100 ml of N-methylpyrrolidone to obtain a solution of 20 to 20 It was added dropwise to the reaction mixture at 23 ° C over 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 Torr. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor was filtered and removed, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure to obtain a polyimine precursor (A-4). As a result of GPC measurement of the polyimine precursor (A-4), the weight average molecular weight (Mw) was 22,000 as a value in terms of polystyrene. [Chemical Formula 65]

(Synthesis Example 5) [From 4,4'-oxydiphthalic dianhydride, m-toluidine, N-(4'-ethynylphenyl)-3,5-diaminobenzamide Synthesis of (Compound (1)-1) and Polyethylenimine Precursor of 2-Hydroxyethyl Methacrylate (A-5: Polyethylenimine Precursor with Radical Polymerizable Group)] Synthesis Example 1 The same operation as in Synthesis Example 1 was carried out except that 9.403 g (46.96 mmol) of 4,4'-oxydiphenylamine was changed to 9.970 g (46.96 mmol) of m-toluidine. Amine precursor (A-5). As a result of GPC measurement of the polyimine precursor (A-5), the weight average molecular weight (Mw) was 21,000 as a value in terms of polystyrene. The molar ratio of the repeating unit described below (repeating unit on the left side: repeating unit on the right side) is 80:20. [Chemical Formula 66]

(Synthesis Example 6) [From 4,4'-oxydiphthalic dianhydride, 4,4'-oxydiphenylamine, N-(4'-ethynylphenyl)-3,5-diamino group Synthesis of benzamide (compound (1)-2) and polyethylenimine precursor of 2-hydroxyethyl methacrylate (A-6: polyethylenimine precursor having radical polymerizable group) 2.950 g (11.74 mmol) of N-(3'-ethynylphenyl)-3,5-diaminobenzamide of Synthesis Example 1 was changed to 2.950 g (11.74 mmol) N-(4) A polyimine precursor (A-6) was obtained in the same manner as in Synthesis Example 1, except that the compound was subjected to the same procedure as in Synthesis Example 1. As a result of GPC measurement of the polyimine precursor (A-6), the weight average molecular weight (Mw) was 25,000 as a value in terms of polystyrene. The molar ratio of the repeating unit described below (repeating unit on the left side: repeating unit on the right side) is 80:20. [Chemical Formula 67]

(Synthesis Example 7) [From 4,4'-oxydiphthalic dianhydride, 4,4'-oxydiphenylamine, N-(3', 5'-diethynylphenyl)-3,5 a polyamidiamine precursor of diaminobenzimidamide (compound (1)-10) and 2-hydroxyethyl methacrylate (A-7: a polyimide intermediate having a radical polymerizable group) Synthesis] 2.950 g (11.74 mmol) of N-(3'-ethynylphenyl)-3,5-diaminobenzamide of Synthesis Example 1 was changed to 3.232 g (11.74 mmol) In the same manner as in Synthesis Example 1, except that N-(3',5'-diethynylphenyl)-3,5-diaminobenzamide was obtained, a polyimine precursor was obtained. A-7). As a result of GPC measurement of the polyimine precursor (A-7), the weight average molecular weight (Mw) was 26,000 as a value in terms of polystyrene. The molar ratio of the repeating unit described below (repeating unit on the left side: repeating unit on the right side) is 80:20. [Chemical Formula 68]

(Synthesis Example 8) [From 4,4'-oxydiphthalic dianhydride, 4,4'-oxydiphenylamine, 1-(3-ethynylphenyl)-3-(3,5-di Aminophenyl)ureido (Compound (1)-24) and a polyamidiamine precursor of 2-hydroxyethyl methacrylate (A-8: Polyethylenimine precursor having a radical polymerizable group) Synthesis] 2.950 g (11.74 mmol) of N-(3'-ethynylphenyl)-3,5-diaminobenzamide of Synthesis Example 1 was changed to 2.950 g (11.74 mmol) In the same manner as in Synthesis Example 1, except that the (3-ethynylphenyl)-3-(3,5-diaminophenyl)ureido group was obtained, a polyimine precursor (A- 8). As a result of GPC measurement of the polyimine precursor (A-8), the weight average molecular weight (Mw) was 19,000 as a value in terms of polystyrene. The molar ratio of the repeating unit described below (repeating unit on the left side: repeating unit on the right side) is 80:20. [Chemical Formula 69]

(Synthesis Example 9) [Polyimine precursor derived from 4,4'-oxydiphthalic dianhydride, 4,4'-oxydiphenylamine and 2-hydroxyethyl methacrylate (for comparison example) Synthesis of polymer R-1: polyethylenimine precursor having a radical polymerizable group] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (at 140 ° C) Dried for 12 hours), 18.6 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine, 140 g of diglyme, mixed at 60 ° C The diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate was produced by stirring for 18 hours. Next, the reaction mixture was cooled to -10 ° C, and while maintaining the temperature at -10 ± 4 ° C, 16.12 g (135.5 mmol) of SOCl _{2 was} added over 10 minutes. After diluting with 50 ml of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution obtained by dissolving 11.75 g (58.70 mmol) of 4,4'-oxydiphenylamine in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20 to 23 ° C for 20 minutes. Next, the reaction mixture was stirred at room temperature for 1 Torr. Next, the polyimide precursor was precipitated in 5 liters of water, and the water-polyimine precursor mixture was stirred at 5000 rpm for 15 minutes. The polyimine precursor was filtered and removed, stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimine precursor was dried at 45 ° C for 3 days under reduced pressure to obtain a polyimine precursor (R-1) for comparative use. As a result of GPC measurement of the polyimine precursor (R-1), the weight average molecular weight (Mw) was 25,000 as a value in terms of polystyrene. [Chemical Formula 70]

<Examples and Comparative Examples> The components described below were mixed, and a coating liquid of a photosensitive resin composition was prepared as a uniform solution. <Composition of Photosensitive Resin Composition> Polyimine precursor: The polyimine precursor described in Table 1 or Table 2 is a photo-radical polymerization of the mass parts described in Table 1 or Table 2 Starting agent: The photoradical polymerization initiator described in Table 1 or Table 2 is a mass fraction of a radically polymerizable compound described in Table 1 or Table 2: the freedom described in Table 1 or Table 2 The base polymerizable compound is a component of the mass component described in Table 1 or Table 2: the components other than those described in Table 1 or Table 2 are the mass parts described in Table 1 or Table 2.

[Table 1] [Table 2]

(B) Radical polymerization initiator B-1: IRGACURE OXE 01 (manufactured by BASF Corporation) B-2: IRGACURE OXE 02 (manufactured by BASF Corporation) B-3: IRGACURE 369 (manufactured by BASF Corporation)

(C) Radical Polymerizable Compound C-1: Dipentaerythritol Hexa(meth)acrylate, A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.) C-2: SR-209 (manufactured by Sartomer Company, Inc.) ) [Chemical Formula 71] C-3: dipentaerythritol tetraacrylate, A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)

(D) Polymerization inhibitor D-1: 2,6-di-t-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) D-2: p-benzoquinone (Tokyo Chemical Industry Co.) , Ltd.) D-3: p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) (E) migration inhibitor E-1: the following compound E-2: the following compound E-3: Compound E-4: the following compounds

(F) Metal adhesion improver F-1: The following compounds F-2: the following compounds F-3: the following compounds

[Chemical Formula 72]

(G) base generator G-1 (photobase generator): the following compound [Chemical Formula 73] G-2 (photobase generator): the following compound [Chemical Formula 74] G-3 (thermobase generator): the following compound [Chemical Formula 75]

(H) Solvent H-1: γ-butyrolactone (manufactured by SANWAYUKA INDUSTRY CORPORATION) H-2: dimethyl hydrazine (manufactured by Wako Pure Chemical Industries, Ltd.) H-3: N-methyl-2-pyrrolidone (made by Ashland Inc.)

<Evaluation><<Elongation at break>> After each photosensitive resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm, the photosensitive resin composition was coated by a spin coating method. The cloth is placed on the wafer. The tantalum 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 20 μm on the tantalum wafer. Using a stepping machine (Nikon NSR 2005 i9C), the photosensitive resin composition layer on the ruthenium wafer was exposed at an exposure wavelength of 365 nm at an exposure energy of 500 mJ/cm ² under a nitrogen atmosphere at 10 ° C / After the temperature rise rate of the minute was raised to 250 ° C, the exposed photosensitive resin composition layer (resin layer) was heated for 3 hours. The cured resin layer was immersed in a 4.9 mass% hydrofluoric acid solution, and the resin layer was peeled off from the tantalum wafer to obtain a resin layer (cured film).

The elongation at break of the resin layer (cured film) obtained in the above was determined as follows. First, the resin layer (cured film) which was peeled off in the above was cut into a film shape having a width of 10 mm and a length of 50 mm, and the crosshead speed was set to 300 mm/min by a tensile tester (TENSILON), and the long side (length) of the film was obtained. In the direction and width direction, the elongation at break was measured in accordance with JIS-K6251 in an environment of 25 ° C and 65% relative humidity (RH). The measurement of the elongation at break in the longitudinal direction and the width direction was carried out five times each. The average value of the elongation at break in the longitudinal direction and the width direction is defined as the elongation at break. A: More than 80%. B: more than 70% and less than 80%. C: more than 60% and 70% or less. D: more than 50% and less than 60%. E: 50% or less.

<<Exposure latitude>> After each photosensitive resin composition was passed through a filter having a pore width of 0.8 μm and subjected to pressure filtration at a pressure of 0.3 MPa, the photosensitive resin composition was coated by a spin coating method. The cloth is on the wafer. The tantalum wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ° C for 5 minutes to form a photosensitive resin composition layer having a uniform thickness of 10 μm on the tantalum wafer. The photosensitive resin composition layer on the germanium wafer was exposed using a stepper (Nikon NSR 2005 i9C). The exposure is performed using i-rays, and at a wavelength of 365 nm, each exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ/cm ² is performed from 5 μm to 25 μm using a line mask of 1 μm increments of lines and spaces. The resin layer was obtained by exposure.

The resin layer obtained above was subjected to negative development for 60 seconds using cyclopentanone. The smaller the line width of the obtained resin layer (pattern), the larger the difference in solubility of the light-irradiating portion and the non-irradiated portion with respect to the developer, and the better the result. Further, when the change in the exposure light is small, the change in the line width is small, indicating that the exposure latitude is large, and this is a preferable result. The measurement limit was 5 μm. A: 5 μm or more and 8 μm or less. B: more than 8 μm and 10 μm or less. C: more than 10 μm and 15 μm or less. D: more than 15 μm and 20 μm or less. E: more than 20 μm. F: A pattern having a line width with edge sharpness was not obtained.

<<Peel defect evaluation (interlayer adhesion)>><<<Production of laminated body (1)>>> Each photosensitive resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm. Thereafter, the photosensitive resin composition was applied onto the tantalum wafer by a spin coating method. The tantalum 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 tantalum wafer. Next, using a stepping machine (Nikon NSR 2005 i9C), the photosensitive resin composition layer on the ruthenium wafer was exposed at an exposure wavelength of 365 nm at an exposure energy of 500 mJ/cm ² , and developed with cyclopentanone for 60 seconds. A hole having a diameter of 10 μm was formed. Subsequently, the temperature was raised at a temperature elevation rate of 10 ° C /min in a nitrogen atmosphere to 250 ° C, and then heated for 3 hours. After cooling to room temperature, the same photosensitive resin composition as that of the above-mentioned photosensitive resin composition was used again on the surface of the resin layer, and the photosensitive resin composition was again filtered to the patterned film in the same manner as described above. A layered body (1) having two resin layers was formed by a 3-hour heating process.

<<<Production of the laminated body (2)>>> The surface of the laminated body (1) obtained above is the same as the photosensitive resin composition used for the production of the laminated body (1). The resin composition was produced by the same process as the production of the laminated body (1), and a laminate (2) having four resin layers was produced.

<<<Production of the laminated body (3)>>> The photosensitive resin composition was subjected to pressure filtration through a filter having a pore width of 0.8 μm, and then the photosensitive resin was spin-coated. The composition is applied to a tantalum wafer. The tantalum 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 tantalum wafer. The photosensitive resin composition layer on the ruthenium wafer was exposed with an exposure energy of 500 mJ/cm ² using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin was exposed with cyclopentanone) The layer was developed for 60 seconds to form a hole having a diameter of 10 μm. Subsequently, the temperature was raised at a temperature elevation rate of 10 ° C /min in a nitrogen atmosphere to 250 ° C, and then heated for 3 hours. After cooling to room temperature, a copper thin layer (metal layer) having a thickness of 2 μm was formed by vapor deposition on a part of the surface of the photosensitive resin composition layer so as to cover the above-mentioned pore portion. Further, on the surface of the metal layer and the photosensitive resin composition layer, the same photosensitive resin composition was used again, and the photosensitive resin composition was again filtered and heated to the patterned film for 3 hours in the same manner as described above. A laminate (3) composed of a resin layer/metal layer/resin layer was produced by the process.

<<<Production of the laminated body (4)>>> On the surface of the laminated body (3), a copper thin layer (metal layer) and a resin layer were alternately produced by the same method as the laminated body (3). A laminate (4) composed of a resin layer/metal layer/resin layer/metal layer/resin layer/metal layer/resin layer.

<<<Release defect evaluation A (without heat treatment)>>> The resin layer of each of the laminates obtained above was cut out so that the resin layer and the resin layer were joined in such a manner that the width in the vertical direction was 5 mm. When the metal layer and the resin layer were in contact with each other, it was confirmed by optical microscopy whether or not peeling occurred between the resin layer/resin layer and the metal layer/resin layer in one slice when viewed from the cross section. Further, the magnification is appropriately adjusted depending on the size of the peeled portion. The occurrence of peeling was confirmed irrespective of the peeling between the resin layer/resin layer and the metal layer/resin layer, and the number of the entire peeling was confirmed. If there was no occurrence of peeling, it showed excellent adhesion and was a preferable result. A: No peeling occurred B: 1 to 2 peeling occurred C: 3 to 5 peeling occurred D: 6 or more peeling occurred

<<<Peel Defect Evaluation B (after heat treatment)>>> Each of the laminates obtained above was heated at 300 ° C for 3 hours in nitrogen. Then, the resin layer of each laminated body was cut into a portion where the resin layer and the resin layer were in contact with each other, and the portion where the metal layer and the resin layer were in contact with each other, and the optical layer was confirmed by an optical microscope. When the cross section is observed, there is no peeling between the resin layer/resin layer and the metal layer/resin layer in one slice. The occurrence of peeling was confirmed irrespective of the peeling between the resin layer/resin layer and the metal layer/resin layer, and the number of the entire peeling was confirmed. If there was no occurrence of peeling, it showed excellent adhesion and was a preferable result. A: No peeling occurred B: 1 to 2 peeling occurred C: 3 to 5 peeling occurred D: 6 or more peeling occurred [Table 3] The numbers of 200 to 800 of the exposure latitude in Table 3 above indicate the exposure energy (unit: mJ/cm ² ).

[Table 4]

[table 5]

<Example 100> The photosensitive resin composition of Example 1 was passed through a filter having a pore width of 0.8 μm and subjected to pressure filtration at a pressure of 0.3 MPa, and then spin-coated thereon to form a thin layer of copper on the surface. On the substrate (3500 rpm, 30 seconds). The photosensitive resin composition applied to the substrate was dried at 100 ° C for 5 minutes, and then exposed using an exposure machine (Karl-Suss MA150). The exposure was performed by irradiating light having a wavelength of 365 nm from a high pressure mercury lamp. After the exposure, the image was developed with cyclopentanone for 75 seconds. Then, it was heated at 180 ° C for 20 minutes. Thus, an interlayer insulating film for a rewiring layer is formed. The interlayer insulating film for the rewiring layer is excellent in absolute properties. Moreover, as a result of manufacturing a semiconductor device using the interlayer insulating film for a rewiring layer, it was confirmed that the operation was normal.

100‧‧‧Semiconductor device

101a～101d‧‧‧ semiconductor components

101‧‧‧Layer

102b～102d‧‧‧through electrodes

103a～103e‧‧‧Metal bumps

105‧‧‧Rewiring layer

110, 110a, 110b‧‧‧ underfill layer

115‧‧‧Insulation film

120‧‧‧Wiring substrate

120a‧‧‧ surface electrode

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

Claims (25)

A photosensitive resin composition containing a polyimine precursor comprising a repeating unit represented by the following formula (1) and a photoradical polymerization initiator; (1) In the formula (1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent group. An organic group; wherein a terminal represented by the following formula (2) is bonded to a terminal of at least one of R ¹¹¹ , R ¹¹³ , R ¹¹⁴ and R ¹¹⁵ ; In the formula (2), R ¹ represents a hydrogen atom or a substituent, and * is a bonding site with R ¹¹¹ , R ¹¹³ , R ¹¹⁴ or R ¹¹⁵ . The photosensitive resin composition according to claim 1, wherein the polyimine precursor has a structure derived from a compound represented by the following formula (3); In the formula (3), A represents a (p+q) valent group; R ¹ represents a hydrogen atom or a substituent; p represents an integer of 1 to 5; and q represents an integer of 2 or more. The photosensitive resin composition according to claim 1, wherein the polyimine precursor has a structure derived from a compound represented by the following formula (3a); In the formula (3a), A ⁰ represents a (l+m) valent group; A ¹ represents a single bond or a (n+1) valent group; R ¹ represents a hydrogen atom or a substituent; and Ar represents a (a+1) valence. The aromatic hydrocarbon group or the aromatic heterocyclic group; a, 1, m and n each independently represent an integer of 1 to 5; wherein at least one of m and n represents an integer of 2 or more. The photosensitive resin composition according to claim 1, wherein the polyimine precursor has a structure derived from a compound represented by the following formula (3b); In the formula (3b), A ⁰ represents a (l+m) valent group; R ¹ represents a hydrogen atom or a substituent; and a, l, m and n each independently represent an integer of 1 to 5; wherein, m and n are At least one of them represents an integer of 2 or more. The photosensitive resin composition according to any one of claims 1 to 4, wherein in the above formula (1), a group represented by the formula (2) is bonded to at least a terminal of the R ¹¹¹ . The photosensitive resin composition according to any one of claims 1 to 4, wherein the polyimine precursor further comprises a repeating unit represented by the formula (1-1); 1) In the formula (1-1), A ¹ and A ² each independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or A monovalent organic group; wherein the repeating unit represented by the formula (1-1) does not contain a group represented by the above formula (2). The photosensitive resin composition according to claim 6, wherein R ¹¹¹ in the above formula (1-1) is represented by -Ar-L-Ar-, wherein each of Ar is independently an aromatic hydrocarbon group, L It is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, and a group containing a combination of two or more of the foregoing. The photosensitive resin composition according to claim 6, wherein R ¹¹¹ in the above formula (1-1) is a group represented by the following formula (51) or (61); In the formula (51), R ¹⁰ to R ¹⁷ are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ¹⁰ to R ¹⁷ is a fluorine atom, a methyl group, a fluoromethyl group or a difluoromethyl group. Or trifluoromethyl; formula (61) In the formula (61), R ¹⁸ and R ¹⁹ each independently represent a fluorine atom, a fluoromethyl group, a difluoromethyl group or a trifluoromethyl group. The photosensitive resin composition according to any one of claims 1 to 4, wherein at least one of R ¹¹³ and R ¹¹⁴ contains a radical polymerizable group. The photosensitive resin composition according to any one of claims 1 to 4, wherein R ¹¹⁵ is a tetravalent organic group containing an aromatic ring. The photosensitive resin composition as described in any one of Claims 1 to 4 which further contains a radically polymerizable compound. The photosensitive resin composition according to any one of claims 1 to 4, further comprising an alkali generating agent. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a solvent. The photosensitive resin composition according to any one of the items 1 to 4, which is used for negative development. The photosensitive resin composition as described in any one of Claims 1 to 4 is used for formation of the 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 15. A laminate having two or more cured films as described in claim 16 of the patent application. The laminate according to claim 17, wherein a metal layer is provided between the cured films. A method for producing a cured film, which comprises the use of the photosensitive resin composition according to any one of claims 1 to 15. The method for producing a cured film according to claim 19, comprising: a process for forming a photosensitive resin composition layer, applying the photosensitive resin composition to a substrate to form a layer; and exposing the process to the foregoing The photosensitive resin composition layer is subjected to exposure; and a development processing process is performed to develop the photosensitive resin composition layer exposed as described above. The method for producing a cured film according to claim 20, wherein the developing treatment is a negative development treatment. The method for producing a cured film according to claim 20, wherein after the developing treatment process, the developed photosensitive resin composition layer is heated at a temperature of 50 to 450 °C. Process. The method for producing a cured film according to any one of the preceding claims, wherein the cured film has a thickness of 1 to 30 μm. In the method for producing a cured film according to any one of the items 19 to 23, after the cured film is formed, the photosensitive resin composition layer is further formed into a process, and the method is the same. The exposure process and the aforementioned development process are sequentially performed 2 to 5 times. A semiconductor device comprising the cured film of claim 16 or the laminate according to claim 17 or claim 18.