Photosensitive resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, and semiconductor device

Abstract

Provided are: a photosensitive resin composition which contains a photosensitizing agent and at least one resin that is selected from the group consisting of polyimide precursors and polyimides, and which satisfies the requirements (i) to (v) described below; a cured product; a laminate; a method for producing a cured product; a method for producing a laminate; a method for producing a semiconductor device; and a semiconductor device. (i) The transmittance at a wavelength of 365 nm is 20% or more. (ii) The film dissolution rate is 0.8 µm / sec or less. (iii) The ethylenically unsaturated group value of the resin is 2.3 mmol / g or less. (iv) The elongation at break of a cured product thereof is 60% or more. (v) The Young's modulus of a cured product thereof is 3.5 GPa or more.

Description

Photosensitive resin composition, cured product, laminate, method for manufacturing a cured product, method for manufacturing a laminate, method for manufacturing a semiconductor device, and semiconductor device

[0001] The present invention relates to a photosensitive resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.

[0002] In modern times, resin materials manufactured from photosensitive resin compositions containing resins are utilized in various fields. For example, polyimide is used in a wide range of applications due to its excellent heat resistance and insulation properties. While not limited to these applications, examples of its use in semiconductor devices for packaging include its use as an insulating film, encapsulant, or protective film. It is also used as a base film or coverlay for flexible substrates.

[0003] For example, in the applications described above, polyimide is used in the form of a photosensitive resin composition containing polyimide or a polyimide precursor. Such a photosensitive resin composition can be applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. The polyimide precursor is cyclized, for example by heating, and becomes polyimide in the cured product. Since the photosensitive resin composition can be applied by known coating methods, it can be said to have excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application position of the photosensitive resin composition to be applied. In addition to the high performance of polyimide, the industrial application development of the above-mentioned photosensitive resin composition is increasingly expected from the viewpoint of such excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a laminate and a photosensitive resin composition used in the manufacture of the laminate, each of which is independently in contact with the other resin layer on at least a portion of its film surface, each independently having a Young's modulus greater than 2.8 GPa and less than or equal to 5.0 GPa, and an elongation at break greater than 50% and less than or equal to 200%, and further having a three-dimensional radical crosslinking structure, and at least one of the resin layers containing at least one of polyimide and polybenzoxazole.

[0005] International Publication No. 2017 / 146152

[0006] For photosensitive resin compositions used to obtain cured products, the cured products obtained from these compositions are required to have excellent resolution and TCT (Thermal Cycle Test) crack resistance. Excellent resolution means that fine patterns can be formed. Excellent TCT crack resistance means that cracks are unlikely to occur between the cured product and the substrate even after a harsh TCT test (for example, repeating -55°C and 200°C for 1000 cycles).

[0007] The present invention aims to provide a photosensitive resin composition that yields a cured product with excellent resolution and excellent TCT crack resistance, a cured product obtained by curing the above photosensitive resin composition, a laminate containing the above cured product, a method for manufacturing the above cured product, a method for manufacturing the above laminate, a method for manufacturing a semiconductor device including the method for manufacturing the above cured product, and a semiconductor device containing the above cured product.

[0008] Examples of typical embodiments of the present invention are shown below. <1> A photosensitive resin composition containing at least one resin selected from the group consisting of a polyimide precursor and a polyimide, and a photosensitizer, satisfying the following (i) to (v). (i) When a coating film with a thickness of 7.5 μm is formed and the transmittance of the coating film at a wavelength of 365 nm is measured, the result is 20% or more. (ii) When a coating film is formed, the following film dissolution rate calculated from the film thickness X of the coating film and the time BT until the coating film is completely dissolved by cyclopentanone is 0.8 μm / sec or less. Exposure pre-coating film thickness X (μm) / BT (sec) = Film dissolution rate (μm / sec). (iii) The ethylenically unsaturated group value of the above resin is 2.3 mmol / g or less. (iv) The elongation at break of the cured product obtained by curing the above photosensitive resin composition is 60% or more. (v) The Young's modulus of the cured product obtained by curing the above photosensitive resin composition is 3.5 GPa or more. <2> The photosensitive resin composition according to <1>, containing a photo radical polymerization initiator as the above photosensitizer. <3> The photosensitive resin composition according to <2>, containing a keto-oxime compound as the above photo radical polymerization initiator. <4> The photosensitive resin composition according to <2> or <3>, wherein the photo radical polymerization initiator contains a compound represented by the following formula (PI-1). In the formula (PI-1), R Ｐ１ represents a monovalent organic group, and R Ｐ２ represents an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, or an alkylaminocarbonyl group, and R Ｐ３ represents an aryl group. <5> The photosensitive resin composition according to any one of <1> to <4>, wherein the above resin contains at least one of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the formula (2-1). In the formula (1-1), A １ and A ２ each independently represents an oxygen atom or -NR ｚ -, R ｚ represents a hydrogen atom or a monovalent organic group, X １ represents an organic group having 4 or more carbon atoms, Y １ represents an organic group having 4 or more carbon atoms, R １ and R ２Each of these independently represents a hydrogen atom or a monovalent organic group. In formula (2-1), X ２ represents an organic group with 4 or more carbon atoms, Y ２ represents an organic group having 4 or more carbon atoms. <6> The photosensitive resin composition according to <5>, wherein the resin comprises at least one of the following repeating unit 1-A and the following repeating unit 2-A. Repeating unit 1-A: A repeating unit represented by the above formula (1-1), where X １ Repeating unit 2-A: A repeating unit represented by the following formula (X-1), where X ２ The repeating unit is represented by the following formula (X-1). In formula (X-1), * independently represents a bonding site with a carbonyl group. <7> The photosensitive resin composition according to <6>, wherein the total content of repeating unit 1-A and repeating unit 2-A relative to the total repeating units of the resin is 10 mol% or more. <8> The photosensitive resin composition according to <5>, wherein the total content of the following repeating unit 1-A, repeating unit 2-A, repeating unit 1-B, repeating unit 2-B, repeating unit 1-C, and repeating unit 2-C in the resin is 99 mol% or more. Repeating unit 1-A: A repeating unit represented by the above formula (1-1), where X １ Repeating unit 2-A: A repeating unit represented by the following formula (X-1), where X ２ Repeating unit 1-B: A repeating unit represented by the following formula (X-1), where X １ Repeating unit 2-B: A repeating unit represented by the following formula (X-2), where X ２ Repeating unit 1-C: A repeating unit represented by the following formula (X-2), where X １ Repeating unit 2-C: A repeating unit represented by the following formula (X-3), where X ２ The repeating unit is represented by the following formula (X-3). In formula (X-1), each * independently represents a bonding site with a carbonyl group. In formula (X-2), * independently represents a bonding site with a carbonyl group. In formula (X-3), * independently represents a bonding site with a carbonyl group. <9> The above resin contains the repeating unit represented by formula (1-1), and all repeating units represented by formula (1-1) contain R １ and R ２ R for all of １ or R ２ A photosensitive resin composition according to any one of <5> to <8>, wherein the proportion of a structure represented by the following formula (R-1) is 50 to 90 mol%. In equation (R-1), * represents A in equation (1-1). １ Or A ２ This represents the bonding site with. <10> The photosensitive resin composition according to any one of <5> to <9>, wherein the resin comprises at least one of the following repeating unit 1-D and the following repeating unit 2-D. Repeating unit 1-D: A repeating unit represented by the above formula (1-1), Y １ Repeating unit 2-D: A repeating unit represented by the following formula (Y-1) or formula (Y-2), Y ２ A repeating unit whose base is represented by the following formula (Y-1) or formula (Y-2). In formula (Y-1), * independently represents a bonding site with a nitrogen atom. In formula (Y-2), * independently represents a bonding site with a nitrogen atom. <11> The photosensitive resin composition according to <10>, wherein the resin comprises at least one of the following repeating unit 1-E and the following repeating unit 2-E. Repeating unit 1-E: A repeating unit represented by the above formula (1-1), Y １ Repeating unit 2-E: A repeating unit represented by the above formula (Y-2), where Y ２A repeating unit in which is the group represented by the above formula (Y-2) <12> The photosensitive resin composition according to any one of <1> to <11>, wherein the content of fluorine atoms in the resin is 0.01 mmol / g or less. <13> The photosensitive resin composition according to any one of <1> to <12>, further comprising a photochromic compound. <14> The photosensitive resin composition according to <13>, wherein the photochromic compound is a compound represented by any of the following formulas (A-b-1) to (A-b-6). In formula (Ab-1), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, R ４ R is a hydrogen atom or any organic group, ５ R is a hydrogen atom or any organic group, ４ and R ５ They may bond to form a ring structure, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, Z １ -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, the dashed line represents a single bond or a double bond, and if the dashed line represents a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A-b-2) or equation (A-b-3), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ha = C(R Ｚ ) - or = N -, R Ｚ L is a hydrogen atom or any organic group. ２ is any divalent linking group which may have substituents, and Z １ is -O, -S, or -NR ６ And, if the dashed line indicates a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A - b - 4), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ ha = C(R Ｚ ) - or = N -, R Ｚ L is a hydrogen atom or any organic group. ２ is any divalent linking group which may have substituents, and Z ２ =O, =S, or =NR ７ And R ７ is a hydrogen atom or any organic group, and the dashed part is a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A-b-5) or equation (A-b-6), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ ha = C(RＺ is - or = N -, and R Ｚ is a hydrogen atom or any organic group, and L ２ is any divalent linking group which may have a substituent, and Z ４ is one of -OH, -SH, -N(R ６ )H, and R ６ is a hydrogen atom or any organic group, An is a counter anion. When the dashed line part is a double bond, or when Rs ２ are bonded to each other to form an aromatic ring, two Rs ３ do not exist. <15> At least one resin selected from the group consisting of a polyimide precursor and a polyimide, the resin containing at least one of a repeating unit represented by the following formula (1-1) and a repeating unit represented by the formula (2-1), and a photosensitizer, and all of Xs １ in the following formula (1-1) and Xs ２ in the formula (2-1) in the resin, the proportion of X １ or X ２ having a structure represented by the following formula (X-1) is 10 to 40 mol%, and the proportion of X １ or X ２ having a structure represented by the following formula (X-2) is 60 to 90 mol%, and all of Ys １ in the following formula (1-1) and Ys ２ in the formula (2-1) in the resin, the proportion of Y １ or Y ２ having a structure represented by the following formula (Y-2) is 80 to 100 mol%, and when the repeating unit represented by the above formula (1-1) is included, all of Rs １ and Rs ２ in the repeating unit represented by all the formulas (1-1), the proportion of R １ or R ２ having a structure represented by the following formula (R-1) is 50 to 90 mol% of the photosensitive resin composition. In the formula (1-1), A １ and A ２ each independently represents an oxygen atom or -NR ｚ -, and R ｚrepresents a hydrogen atom or a monovalent organic group, X １ represents an organic group with 4 or more carbon atoms, Y １ R represents an organic group with 4 or more carbon atoms. １ and R ２ Each of these independently represents a hydrogen atom or a monovalent organic group. In formula (2-1), X ２ represents an organic group with 4 or more carbon atoms, Y ２ This represents an organic group with four or more carbon atoms. In formula (X-1), each * independently represents a bonding site with a carbonyl group. In formula (X-2), * represents each independent site of attachment to a carbonyl group. In formula (Y-2), each * independently represents a bonding site with a nitrogen atom. In equation (R-1), * represents A in equation (1-1). １ Or A ２ This represents the bonding site with. <16> A photosensitive resin composition according to any one of <1> to <15>, used for forming an interlayer insulating film for a redistribution layer. <17> A cured product obtained by curing a photosensitive resin composition according to any one of <1> to <11>. <18> A laminate comprising two or more layers made of the cured product according to <17>, with a metal layer between any of the layers made of the cured product. <19> A method for producing a cured product, comprising a film forming step of applying a photosensitive resin composition according to any one of <1> to <8> and 15> onto a substrate to form a film. <20> A method for producing a cured product according to <19>, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern. <21> A method for producing a cured product according to <19> or <20>, comprising a heating step of heating the film at 50 to 450°C. <22> A method for producing a laminate, comprising a method for producing a cured product according to any one of <19> to <21>. <23> A method for manufacturing a semiconductor device, comprising a method for manufacturing a cured product described in any one of <19> to <21>. <24> A semiconductor device comprising the cured product described in <17>.

[0009] The present invention provides a photosensitive resin composition that yields a cured product with excellent resolution and excellent TCT crack resistance, a cured product obtained by curing the photosensitive resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product.

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, preferred embodiments are more preferred embodiments.

[0011] (Photosensitive resin composition) The photosensitive resin composition according to the first aspect of the present invention (hereinafter also referred to as the "first photosensitive resin composition") comprises at least one resin selected from the group consisting of polyimide precursors and polyimides, and a photosensitive agent, and satisfies the following (i) to (v). (i) A coating film with a thickness of 7.5 μm is formed, and the transmittance of the coating film at a wavelength of 365 nm is measured to be 20% or more. (ii) A coating film is formed, and the following film dissolution rate, calculated from the film thickness X of the coating film and the time BT until the coating film is completely dissolved by cyclopentanone, is 0.8 μm / sec or less: Film thickness X (μm) / BT (sec) = Film dissolution rate (μm / sec) (iii) The ethylenically unsaturated value of the resin is 2.3 mmol / g or less. (iv) The elongation at break of the cured product obtained by curing the photosensitive resin composition is 60% or more. (v) The Young's modulus of the cured product obtained by curing the photosensitive resin composition is 3.5 GPa or more.

[0012] A photosensitive resin composition according to a second aspect of the present invention (hereinafter also referred to as the "second photosensitive resin composition") comprises at least one resin selected from the group consisting of polyimide precursors and polyimides, the resin containing at least one of repeating units represented by formula (1-1) and repeating units represented by formula (2-1), and a photosensitive agent, wherein all X in the following formula (1-1) contained in the resin １ and X in equation (2-1) ２ For all of X １ or X ２ The proportion of structures whose structure is represented by the following formula (X-1) is between 10 and 40 mol%, and X １ or X ２ The proportion of the structure represented by the following formula (X-2) is 60 to 90 mol%, and all of the Y in formula (1-1) contained in the resin is １ and Y in equation (2-1) ２ Y for all of １ or Y ２ If the proportion of structures represented by formula (Y-2) is 80-100 mol%, and includes repeating units represented by formula (1-1), then R is included in all repeating units represented by formula (1-1). １ and R ２R for all of １ or R ２ The proportion of substances whose structure is represented by formula (R-1) is between 50 and 90 mol%.

[0013] Hereinafter, the photosensitive resin composition according to the first aspect of the present invention and the photosensitive resin composition according to the second aspect of the present invention will be collectively referred to as "the photosensitive resin composition of the present invention" or simply as "the photosensitive resin composition." Furthermore, the polyimide precursor and polyimide contained in the photosensitive resin composition according to the first aspect of the present invention will also be referred to as "the first specific resin," and the polyimide precursor and polyimide contained in the photosensitive resin composition according to the second aspect of the present invention will also be referred to as "the second specific resin," and the first specific resin and the second specific resin will be collectively referred to simply as "the specific resin."

[0014] The photosensitive resin composition of the present invention is preferably used to form a photosensitive film subjected to exposure and development, and more preferably used to form a film subjected to exposure and development using a developer containing an organic solvent. The photosensitive resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers. In particular, the use of the photosensitive resin composition of the present invention in forming interlayer insulating films for redistribution layers is one of the preferred embodiments of the present invention. Furthermore, the photosensitive resin composition of the present invention is preferably used to form a photosensitive film subjected to negative-type development. In the present invention, negative-type development refers to development in which unexposed areas are removed by development during exposure and development, and positive-type development refers to development in which exposed areas are removed by development. As the above exposure method, the above developer, and the above development method, for example, the exposure method, the developer, and the development method described in the exposure step, and the development step, respectively, described later in the description of the method for manufacturing cured products, can be used.

[0015] The photosensitive resin composition of the present invention yields a cured product with excellent resolution and TCT crack resistance. The mechanism by which these effects are obtained is unknown, but it is presumed to be as follows.

[0016] The first photosensitive resin composition of the present invention is a photosensitive resin composition that yields a cured product with high i-line transmittance of the coating film, a film dissolution rate that is not too high, a resin with an ethylenically unsaturated value that is not too high, excellent elongation at break, and excellent Young's modulus. Here, the high i-line transmittance and not too high film dissolution rate of the cured product result in a cured product with excellent resolution. By satisfying (i) above, exposure light can easily reach deep into the film, allowing for sufficient curing and reducing the likelihood of shape defects such as thinning of the pattern in the deeper parts. By satisfying (ii) above, swelling of the film during development is suppressed, enabling the formation of finer patterns. Furthermore, by satisfying (iii) above, the increase in molecular weight of the resin, polymerizable compounds, etc. resulting from the crosslinking reaction in the low exposure range is suppressed, resulting in improved contrast and excellent resolution. In addition, by satisfying (iii) above, the crosslinking density in the cured product can be reduced. Generally, resins with a high Young's modulus tend to have strong interactions and are difficult to elongate. However, it is possible to achieve both the Young's modulus in (v) above and the elongation at break in (iv) above, which are in a trade-off relationship. By satisfying (iv) above, it is thought that the cured product itself can easily follow the deformation of the substrate, wiring, etc. due to temperature changes, and cracks are less likely to occur. By satisfying (v) above, it is thought that cracks are less likely to occur because the strength of the cured product itself is high. The present invention is based on the new finding that resolution and TCT crack resistance can be achieved at the same time by considering the balance of such various properties and keeping each within an appropriate range. Furthermore, the second photosensitive resin composition of the present invention contains a specific resin. A cured product made from such a photosensitive resin composition containing a specific resin has high i-ray transmittance, the film dissolution rate of the coating film is not too high, the ethylenically unsaturated value of the resin is not too high, and a cured product with excellent elongation at break and excellent Young's modulus can be obtained. Therefore, for the same reasons as the first photosensitive resin composition, a cured product with excellent resolution and excellent TCT crack resistance can be obtained.

[0017] However, Patent Document 1 does not describe either the first photosensitive resin composition or the second photosensitive resin composition of the present invention.

[0018] The photosensitive resin composition of the present invention will be described in detail below.

[0019] <Conditions (i) to (v)> The first photosensitive resin composition of the present invention satisfies the following conditions (i) to (v). The second photosensitive resin composition of the present invention preferably satisfies the following conditions (i) to (v). (i) A coating film with a thickness of 7.5 μm is formed, and the transmittance of the coating film at a wavelength of 365 nm is measured to be 20% or more. (ii) A coating film is formed, and the following film dissolution rate, calculated from the film thickness X of the coating film and the time BT until the coating film is completely dissolved by cyclopentanone, is 0.8 μm / sec or less: Film thickness X (μm) / BT (sec) = Film dissolution rate (μm / sec) (iii) The ethylenically unsaturated value of the resin is 2.3 mmol / g or less. (iv) The elongation at break of the cured product obtained by curing the photosensitive resin composition is 60% or more. (v) The Young's modulus of the cured product obtained by curing the photosensitive resin composition is 3.5 GPa or more.

[0020] [Condition (i)] In (i) above, from the viewpoint of resolution, the transmittance is preferably 25% or more, more preferably 30% or more, and even more preferably 35% or more. The upper limit of the transmittance is not particularly limited and may be 100% or less. The transmittance in (i) above is measured by the following method: The photosensitive resin composition is applied to a quartz substrate by spin coating, the quartz substrate is dried on a hot plate at 100°C for 5 minutes, a photosensitive resin composition layer (coating film) of uniform thickness of 7.5 μm is formed on the quartz substrate, and the transmittance is measured by a spectrophotometer. If application by spin coating is difficult, known coating methods such as slit coating may be used. Furthermore, if it is difficult to form a coating film with a thickness of 7.5 μm, for example, a coating film with a thickness of 15 μm may be formed, and the obtained transmittance (for example, 90%) may be converted to the value for a 7.5 μm coating film by formula such as 10^-((LOG(100 / 90)) * 7.5 / 15) * 100.

[0021] Furthermore, from the viewpoint of resolution, the transmittance of the specific resin at a wavelength of 365 nm is preferably 20% or more, more preferably 25% or more, even more preferably 30% or more, and particularly preferably 35% or more. The upper limit of the above transmittance is not particularly limited and may be 100% or less.

[0022] The above coating film was subjected to light with a wavelength of 365 nm at a rate of 400 mJ / cm². ２ The transmittance at a wavelength of 365 nm after exposure with the exposure energy is preferably 20% or more, more preferably 25% or more, even more preferably 30% or more, and particularly preferably 35% or more. The upper limit of the above transmittance is not particularly limited and may be 100% or less.

[0023] [Condition (ii)] In the above condition (ii), from the viewpoint of resolution, the film dissolution rate is preferably 0.5 μm / sec or less, more preferably 0.4 μm / sec or less, and even more preferably 0.3 μm / sec or less. The lower limit of the above film dissolution rate is not particularly limited, but from the viewpoint of enabling development, it is preferably 0.1 μm / sec or more. The film dissolution rate in (ii) above is measured by the following method. A photosensitive resin composition is applied to a silicon wafer by spin coating, the silicon wafer is dried on a hot plate at 100°C for 5 minutes, and a photosensitive resin composition layer (coating film) of a uniform thickness of 7.5 μm is formed on the silicon wafer. Using a developer (ACTES ADE-3000) with cyclopentanone as the developer, the time BT until the photosensitive resin composition layer disappears is measured. The disappearance of the photosensitive resin composition layer can be confirmed visually.

[0024] [Condition (iii)] The ethylenically unsaturated value is the amount (molecule) of ethylenically unsaturated groups in 1 g of the specific resin. It is preferable that the ethylenically unsaturated groups be included in the specific resin as radical polymerizable groups. In the above condition (iii), from the viewpoint of achieving both resolution and TCT crack resistance, the ethylenically unsaturated value is preferably 2.2 mmol / g or less, more preferably 2.1 mmol / g or less, and even more preferably 2.0 mmol / g or less. The lower limit of the above ethylenically unsaturated value is not particularly limited, but it is preferably 1.2 mmol / g or more. The ethylenically unsaturated value is measured by the following method. Tetramethylsilane is used as the reference substance, and the specific resin １ The molar amount of polymerizable groups in the resin is calculated from the ratio of the integrated intensity of the peak corresponding to each polymerizable group in the H-NMR chart to the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specified resin.

[0025] [Condition (iv)] In the above condition (iv), from the viewpoint of TCT crack resistance, the elongation at break of the cured product is preferably 62% or more, more preferably 65% ​​or more, and even more preferably 68% or more. The upper limit of the elongation at break is not particularly limited, but it is preferably 100% or less.

[0026] The above cured product is manufactured by the following method: A photosensitive resin composition is applied to a silicon wafer by spin coating, and dried on a hot plate at 100°C for 5 minutes to form a photosensitive resin composition layer with a thickness of 12 μm. The photosensitive resin composition layer is then subjected to a 400 mJ / cm² treatment using an i-line stepper. ２Exposure is performed using a dumbbell-shaped mask with the specified exposure energy. The dumbbell shape is the No. 7 dumbbell shape described in JIS K 6251:2017. Afterwards, development is performed with cyclopentanone for a time of (7.5 μm / the above film dissolution rate) × 1.5 (sec), and then rinsing is performed with PGMEA (propylene glycol monomethyl ether acetate) to remove unexposed areas. Furthermore, under a nitrogen atmosphere, the temperature is increased at a heating rate of 10°C / min and heated to 230°C for 3 hours to obtain a cured product. The cured product is immersed in a 4.9 mass% hydrofluoric acid solution and the dumbbell-shaped cured product (test piece) is peeled off from the silicon wafer. If coating by spin coating is difficult, known coating methods such as the slit coating method may be used. Also, 400 mJ / cm ２ If a good pattern shape cannot be obtained with the exposure energy, the exposure energy may be adjusted as appropriate. Regarding the developer, if development with cyclopentanone is difficult, it may be changed to a known developer as appropriate, depending on the composition of the photosensitive resin composition.

[0027] Furthermore, the elongation at break is measured by the following method: The specimen is subjected to a tensile testing machine (Instron model 5965) at a crosshead speed of 5 mm / min, under conditions of 25°C and 65% RH (relative humidity), and the elongation in the longitudinal direction of the specimen is measured in accordance with JIS-K7161-1 (2014). Each evaluation is performed six times, and the arithmetic mean of the elongation at the time of fracture is taken as the elongation at break described above.

[0028] [Condition (v)] In the above condition (v), from the viewpoint of TCT crack resistance, the Young's modulus of the cured product is preferably 3.6 GPa or higher, more preferably 3.7 GPa or higher, and even more preferably 3.8 GPa or higher. The upper limit of the Young's modulus is not particularly limited, but it is preferably 6.0 GPa or lower. The cured product is manufactured by the same method as the cured product in the above condition (iv). The Young's modulus is measured by the following method: Using a DMA850 (TA Instruments), the measurement is performed in accordance with JIS-K7161-1 (2014) at a crosshead speed of 5 mm / min in an environment of 25°C and 65% RH (relative humidity).

[0029] Here, it is preferable that the photosensitive resin composition of the present invention satisfies the following conditions (vi) to (x): (vi) A coating film with a thickness of 7.5 μm is formed, and the transmittance of the coating film at a wavelength of 365 nm is measured to be 25% or more. (vii) A coating film is formed, and the following film dissolution rate, calculated from the film thickness X of the coating film and the time BT until the coating film is completely dissolved by cyclopentanone, is 0.5 μm / sec or less. Film thickness X before exposure (μm) / BT (sec) = Film dissolution rate (μm / sec) (viiii) The ethylenically unsaturated value of the resin is 2.2 mmol / g or less. (ix) The elongation at break of the cured product obtained by curing the photosensitive resin composition is 65% or more. (x) The Young's modulus of the cured product obtained by curing the photosensitive resin composition is 3.7 GPa or more.

[0030] <First Specific Resin> The first photosensitive resin composition contains at least one resin (the first specific resin) selected from the group consisting of polyimide precursors and polyimides. Preferably, the first photosensitive resin composition contains a polyimide precursor as the first specific resin.

[0031] In this specification, polyimide refers to a resin having repeating units containing imide bonds in its molecular chain, and preferably a resin having repeating units containing imide ring structures in its molecular chain. Furthermore, if the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide bonds in its main chain, and more preferably a resin having repeating units containing imide ring structures in its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chains" refer to the other bonding chains. In this specification, imide bond refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, imide ring structure refers to a ring structure that includes all two carbon atoms and nitrogen atoms in the above imide bond as ring members. The imide ring structure is preferably a five-membered ring. In addition to imide bonds, polyimide may also have amide bonds in its molecular chain, a so-called polyamide imide. In this specification, an amide bond refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Also, # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0032] In this specification, a polyimide precursor refers to a resin that undergoes a change in chemical structure due to external stimuli to become a polyimide, preferably a resin that undergoes a change in chemical structure due to heat to become a polyimide, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a polyimide.

[0033] [Groups having ethylenically unsaturated bonds] The first specific resin contains groups having ethylenically unsaturated bonds. As groups having ethylenically unsaturated bonds, radical polymerizable groups are preferred. Examples of the above-mentioned groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, and maleimide groups. Among these, (meth)acryloyl groups, vinylphenyl groups, or maleimide groups are preferred, and from the viewpoint of reactivity, (meth)acryloyl groups are more preferred. Furthermore, from the viewpoint of reducing dielectric loss tangent, vinylphenyl groups or maleimide groups are preferred. The (meth)acryloyl group is preferably composed of a (meth)acryloxy group or a (meth)acrylamide group, and from the viewpoint of reactivity, it is more preferable to be composed of a (meth)acryloxy group. Furthermore, from the viewpoint of adhesion, hydrophobic vinylphenyl groups are preferred.

[0034] [Repeating unit represented by formula (1-1), repeating unit represented by formula (2-1)] The first specific resin preferably contains at least one of the repeating unit represented by the following formula (1-1) and the repeating unit represented by the following formula (2-1), and more preferably contains the repeating unit represented by the following formula (1-1). In formula (1-1), A １ and A ２ Each of these is independently an oxygen atom or -NR ｚ - represents R ｚ represents a hydrogen atom or a monovalent organic group, X １ represents an organic group with 4 or more carbon atoms, Y １ R represents an organic group with 4 or more carbon atoms. １ and R ２ Each of these independently represents a hydrogen atom or a monovalent organic group. In formula (2-1), X ２ represents an organic group with 4 or more carbon atoms, Y ２ This represents an organic group with four or more carbon atoms.

[0035] [A １ and A ２ A in equation (1) １ and A ２ Each of these is independently an oxygen atom or -NR ＺR represents a negative sign, and an oxygen atom is preferred. Ｚ R represents a hydrogen atom or a monovalent organic group, with a hydrogen atom being preferred. Ｚ When R is a monovalent organic group Ｚ Examples include hydrocarbon groups. Also, A １ ga-NR Ｚ - If R Ｚ is R １ It may bond with to form a ring structure. Examples of the formed ring structure include hydrocarbon rings, with aliphatic hydrocarbon rings being preferred, and saturated aliphatic hydrocarbon rings being more preferred. Furthermore, the above ring structure is preferably a five-membered ring or a six-membered ring. A ２ ga-NR Ｚ - If R Ｚ is R ２ It may combine with to form a ring structure. A preferred embodiment of the formed ring structure is the R described above. Ｚ and R １ This is similar to a preferred embodiment of the ring structure formed by bonding with the other elements.

[0036] [X １ ] In formula (1-1), X １ The number of carbon atoms is preferably 4 to 50, and more preferably 6 to 40.

[0037] X １ It is preferable that the structure is represented by the following formula (X-1). In formula (X-1), each * independently represents a bonding site with a carbonyl group.

[0038] Also, X １ It is preferable that the structure is represented by the following formula (X-2) or formula (X-3). In formula (X-2), each * independently represents a bonding site with a carbonyl group. In formula (X-3), each * independently represents a bonding site with a carbonyl group.

[0039] Other, X １ This may be a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of Japanese Patent Application Publication No. 2023-003421.

[0040] Also, X１ It is preferable that the structure does not contain imide bonds. Also, X １ It is also preferable that the structure does not contain urethane bonds, urea bonds, and amide bonds. In the present invention, urethane bonds are defined as *-O-C(=O)-NR Ｎ -* is a combination represented by R Ｎ R represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom. Ｎ The hydrogen atom or hydrocarbon group is preferred, the hydrogen atom or alkyl group is more preferred, and the hydrogen atom is even more preferred. In the present invention, the urea bond is *-NR Ｎ -C(=O)-NR Ｎ -* is a combination represented by R Ｎ Each of the symbols independently represents a hydrogen atom or a monovalent organic group, and each of the symbols * represents a bonding site with a carbon atom. Ｎ The preferred embodiment is as described above. Furthermore, X １ Preferably, the structure does not contain ester bonds. In the present invention, an ester bond is a bond represented by *-O-C(=O)-*.

[0041] [Y １ ] In formula (1-1), Y １ The number of carbon atoms is preferably 4 to 50, and more preferably 6 to 40.

[0042] Y １ It is preferable that the group is represented by the following formula (Y-1) or formula (Y-2), and more preferably by the group represented by formula (Y-2). In formula (Y-1), each * independently represents a bonding site with a nitrogen atom. In formula (Y-2), each * independently represents a bonding site with a nitrogen atom.

[0043] Also, Y １ The structure may include a group represented by formula (YP-1). In the above embodiment, Y １ It is more preferable that the structure is represented by formula (YP-1). In formula (YP-1), R Ｙ１ and R Ｙ２Each of the symbols independently represents a group having an ethylenically unsaturated bond, L represents a single bond or a divalent linking group that does not contain an imide bond, and * represents a bonding site with another structure.

[0044] In formula (YP-1), R Ｙ１ and R Ｙ２ Each of these is preferably an independent group represented by the following formula (R1-1). In formula (R1-1), L Ｙ１ represents a 1+1 valent linking group, A Ｙ１ represents a polymerizable group, a1 represents an integer of 1 or more, and * represents the bonding site with the aromatic ring in formula (YP-1).

[0045] In formula (R1-1), L Ｙ１ Preferably, the group is represented by the following formula (L-2). In formula (L-2), Z ２ -O-, -NR Ｎ -, -C(=O)O- or -C(=O)NR Ｎ - represents R Ｎ represents a hydrogen atom or a monovalent organic group, and when a1 is 1, L ｘ represents a single bond or a divalent linking group, and when a1 is 2 or more, L ｘ * represents a 1+1 valent linking group, a1 represents an integer greater than or equal to 1, * represents the bonding site with the aromatic ring in formula (YP-1), and # represents A in formula (R1-1). Ｙ１ This represents the connection point.

[0046] In formula (L-2), Z ２ It is preferable that is -O- or -C(=O)O-. Also, Z ２ ga-NR Ｎ - or -C(=O)NR Ｎ - If R Ｎ A hydrogen atom or a hydrocarbon group is preferred, a hydrogen atom, an alkyl group or a phenyl group is more preferred, and a hydrogen atom is even more preferred. In formula (L-2), when a1 is 1, L ｘIt is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group. In formula (L-2), when a1 is 2 or more, L ｘ The group is preferably a hydrocarbon group, a heterocyclic group, or a combination thereof, more preferably a saturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, and even more preferably a saturated aliphatic hydrocarbon group having 3 to 15 carbon atoms. In formula (L-2), a1 is the same as a1 in formula (R1-1).

[0047] In formula (R1-1), A Ｙ１ represents a polymerizable group. The preferred embodiment of the polymerizable group is as described above for the preferred embodiment of the polymerizable group possessed by the first specific resin.

[0048] Among these, A Ｙ１ The group is preferably a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these, and more preferably a maleimide group, a (meth)acryloyl group, or a vinylphenyl group. In particular, from the viewpoint of reactivity, a (meth)acryloyl group is preferred. Furthermore, from the viewpoint of reducing the dielectric loss tangent of the cured product, a maleimide group or a vinylphenyl group is preferred, and a vinylphenyl group is more preferred. In particular, A in formula (R1-1) Ｙ１ At least one of these is preferably a vinylphenyl group, a maleimide group, a (meth)acryloyl group, a vinyl group, an allyl group, an epoxy group, or a group containing these; more preferably a maleimide group, a (meth)acryloyl group, or a vinylphenyl group; and even more preferably a vinylphenyl group.

[0049] Among these, A in equation (R1-1) Ｙ１ is a vinylphenyl group, L Ｙ１ It is preferable that the group is represented by formula (L-2-1) or -C(=O)O-. In formula (L-2-1), L Ｘ２ represents a hydrocarbon group, a1 represents an integer of 1 or more, * represents the bonding site with the aromatic ring in formula (YP-1), and # represents A in formula (R1-1).Ｙ１ This represents the bonding site with. In formula (L-2-1), L Ｘ２ An aliphatic saturated hydrocarbon group is preferred. When a1 is 1, L Ｘ２ An alkylene group is preferred, an alkylene group having 1 to 10 carbon atoms is more preferred, an alkylene group having 1 to 4 carbon atoms is even more preferred, and a methylene group is particularly preferred. In formula (L-2-1), a1 is the same as a1 in formula (R1-1).

[0050] Also, A in equation (R1-1) Ｙ１ The maleimide group is L Ｙ１ is a group represented by formula (L-2), where L in formula (L-2) Ｘ It is preferable that the group is an aromatic group or an aliphatic saturated hydrocarbon group having four or more carbon atoms. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having six to ten carbon atoms, and more preferably an aromatic hydrocarbon group having six carbon atoms. Examples of heteroatoms in the aromatic heterocyclic group include oxygen atoms, nitrogen atoms, sulfur atoms, etc. The number of heteroatoms in the aromatic heterocyclic group is preferably one or two. Furthermore, the aromatic heterocyclic group is preferably a five-membered ring or a six-membered ring containing the above heteroatoms. In addition, other aromatic heterocyclic groups or other aromatic hydrocarbon ring groups may be fused to the aromatic heterocyclic group. The aliphatic saturated hydrocarbon group having four or more carbon atoms may have a linear, branched, cyclic, or combination thereof structure. The number of carbon atoms in the aliphatic saturated hydrocarbon group having four or more carbon atoms is preferably four to 20, and more preferably five to 10.

[0051] In formula (R1-1), a1 is preferably an integer between 1 and 4, and more preferably an integer between 1 and 2. Furthermore, the embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention.

[0052] Furthermore, it is preferable that the number of ester bonds in formula (R-1) is 1 or 0.

[0053] Other, Y １The structure may be as described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421. Also, Y １ It is preferable that the structure does not contain an imide bond. Also, Y １ It is preferable that the structure does not contain urethane bonds, urea bonds, and amide bonds. Among these, Y １ It is preferable that it does not contain imide bonds, urethane bonds, urea bonds, and amide bonds, and more preferably that it does not contain imide bonds, urethane bonds, urea bonds, amide bonds, and ester bonds.

[0054] [R １ and R ２ ] In formula (1-1), R １ and R ２ Each is independently a hydrogen atom or a monovalent organic group, R １ and R ２ Preferably, at least one of them is a monovalent organic group having an ethylenically unsaturated bond. １ and R ２ A preferred embodiment of the present invention is one in which both are monovalent organic groups having an ethylenically unsaturated bond. Preferred monovalent organic groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, groups having a (meth)acryloyloxy group, or groups having a group represented by the following formula (III), with groups having a group represented by the following formula (III) being more preferred. Furthermore, a preferred embodiment of the present invention is one in which the monovalent organic group having an ethylenically unsaturated bond is a group represented by the following formula (III).

[0055]

[0056] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH２ - represents a cycloalkylene group or a polyalkylene oxy group. Preferred R ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH ２ CH(OH)CH ２ -Polyalkylene oxy groups are examples, including alkylene groups such as ethylene groups and propylene groups, and -CH ２ CH(OH)CH ２-, cyclohexyl groups, polyalkylene oxy groups are more preferred, alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have patterns such as alternating arrangements. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, particularly preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc. The number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred configurations for the number of repeating ethylene oxy groups in these groups are as described above.

[0057] In equation (1-1), R １If R is a hydrogen atom, ２ If the atom is a hydrogen atom, the polyimide precursor may form a pair salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0058] Among these, R １ and R ２ It is preferable that the structure is represented by the following formula (R-1). In equation (R-1), * represents A in equation (1-1). １ Or A ２ This represents the connection point.

[0059] Furthermore, the first specific resin includes a repeating unit represented by formula (1-1), and R is included in all repeating units represented by formula (1-1). １ and R ２ R for all of １ or R ２ The proportion of the structure represented by formula (R-1) is preferably 50 to 90 mol%, more preferably 55 to 90 mol%, and even more preferably 60 to 80 mol%.

[0060] In equation (1-1), R １ and R ２ One of the groups may be a monovalent organic group that does not have an ethylenically unsaturated bond. Examples of a monovalent organic group that does not have an ethylenically unsaturated bond include a hydrocarbon group, a heterocyclic group, or at least one of a hydrocarbon group and a heterocyclic group, and -O-, -C(=O)-, -S-, -SO ２ - or - NR ＮGroups represented by a combination with - are preferred, hydrocarbon groups, or groups represented by a combination of a hydrocarbon group and -O- are more preferred, alkyl groups, aromatic hydrocarbon groups, or polyalkylene oxy groups are even more preferred. RN represents a hydrogen atom or a hydrocarbon group, hydrogen atoms or alkyl groups are preferred, hydrogen atoms or methyl groups are more preferred, and hydrogen atoms are even more preferred. The above RN represents a hydrogen atom or a monovalent organic group, hydrogen atoms, hydrocarbon groups, or aromatic groups are preferred, hydrogen atoms or alkyl groups are more preferred, and hydrogen atoms are even more preferred. In this specification, when simply referred to as alkyl groups, alkyl groups include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups. The same applies to alkylene groups, aliphatic hydrocarbon groups, etc.

[0061] Among these, as monovalent organic groups that do not have an ethylenically unsaturated bond, structures represented by any of the following formulas (R-2) to (R-10) are preferred, structures represented by any of the following formulas (R-2), (R-4), (R-7), and (R-9) are more preferred, and the structure represented by the following formula (R-2) is even more preferred. In equations (R-2) to (R-10), * represents A in equation (1-1). １ Or A ２ This represents the connection point.

[0062] [X ２ ] In formula (2-1), X ２ A preferred embodiment is X in formula (1-1) described above. １ This is similar to the preferred embodiment.

[0063] [Y ２ ] In formula (2-1), Y ２ A preferred embodiment is Y in formula (1-1) described above. １ This is similar to the preferred embodiment.

[0064] [Content of repeating units] The first specific resin preferably contains at least one of the following repeating unit 1-A and repeating unit 2-A. Repeating unit 1-A: A repeating unit represented by the above formula (1-1), X １Repeating unit 2-A: A repeating unit represented by the above formula (X-1), where X ２ The repeating unit is represented by the above formula (X-1).

[0065] Here, the total content of repeating unit 1-A and repeating unit 2-A relative to the total repeating units of the first specific resin is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more. The upper limit of the above content is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less.

[0066] The first specific resin preferably contains at least one of the repeating unit 1-A, repeating unit 2-A, repeating unit 1-B, repeating unit 2-B, repeating unit 1-C, and repeating unit 2-C described above. Furthermore, the first specific resin preferably contains the repeating unit 1-A and repeating unit 1-B described above. Repeating unit 1-B: A repeating unit represented by the above formula (1-1), where X １ Repeating unit 2-B: A repeating unit represented by the above formula (X-2), where X ２ Repeating unit 1-C: A repeating unit represented by the above formula (X-2), where X １ Repeating unit 2-C: A repeating unit represented by the above formula (X-3), where X ２ The repeating unit is represented by the above formula (X-3).

[0067] The total content of the repeating unit 1-A, repeating unit 2-A, repeating unit 1-B, repeating unit 2-B, repeating unit 1-C, and repeating unit 2-C in the first specific resin is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more. The upper limit of the above content is not particularly limited and may be 100 mol%.

[0068] The first specific resin preferably contains at least one of the following repeating unit 1-D and repeating unit 2-D. Repeating unit 1-D: A repeating unit represented by the above formula (1-1), Y １ Repeating unit 2-D: A repeating unit represented by the above formula (Y-1) or formula (Y-2), Y ２ Repeating units where the base is represented by the above formula (Y-1) or formula (Y-2)

[0069] The total content of repeating unit 1-D and repeating unit 2-D in the first specific resin is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more. The upper limit of the above content is not particularly limited and may be 100 mol%. Also, for example, X in formula (1-1) １ The structure is represented by equation (X-1), and Y １ The repeating unit whose equation is (Y-2) corresponds to repeating unit 1-A, repeating unit 1-D, and repeating unit 1-E, which will be described later.

[0070] The first specific resin preferably contains at least one of the following repeating unit 1-E and repeating unit 2-E. Repeating unit 1-E: A repeating unit represented by the above formula (1-1), Y １ Repeating unit 2-E: A repeating unit represented by the above formula (Y-2), where Y ２ The repeating unit is represented by the above formula (Y-2).

[0071] The total content of repeating unit 1-E and repeating unit 2-E in the first specific resin is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more. The upper limit of the above content is not particularly limited and may be 100 mol%.

[0072] [Fluorine Atom Content] The fluorine atom content in the first specific resin is preferably 0.01 mmol / g or less, more preferably 0.001 mmol / g or less, and even more preferably 0.0001 mmol / g or less. The lower limit of the above content is not particularly limited and may be 0 mmol / g.

[0073] [Imidification Rate] When the first specific resin is a polyimide precursor, the imidification rate of the first specific resin is preferably less than 70%, more preferably 60% or less, even more preferably 50% or less, even more preferably 40% or less, and particularly preferably 30% or less, from the viewpoint of the film strength and insulating properties of the resulting organic film. The lower limit of the above imidification rate is not particularly limited and may be 0% or more. When the first specific resin is a polyimide, the imidification rate of the first specific resin is preferably 70% or more, more preferably 80% or more, even more preferably 90% or more, even more preferably 95% or more, and particularly preferably 98% or more. The upper limit of the above imidification rate is not particularly limited and may be 100% or less.

[0074] In this invention, the imidization rate is a value calculated by the following method. The resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Other solvents that can be used include solvents contained in photosensitive resin compositions, such as NMP. The viscosity may also be changed as appropriate within an adjustable range. The silicon wafer to which the obtained resin layer has been applied is dried on a hot plate at 100°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 μm on the silicon wafer after film formation. Here, if only a resin solution with low viscosity can be obtained, and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be changed as appropriate. For example, if the film thickness is 5 μm or more, a similar value for the imidization rate can be obtained. The above resin layer was measured using the ATR method with Nicoleti S20 (manufactured by Thermofisher), with a measurement range of 4000-700 cm. －１ The measurement was taken 50 times. 1380 cm －１ Nearby (1350-1450 cm) －１ (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500 cm －１ Nearby (1460-1550 cm) －１ The imidization index A of the resin is calculated by dividing the value by the peak height of the peak with the maximum peak intensity (if there are multiple peaks) and heating the film at 350°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min. The imidization index B is calculated in the same manner and the value obtained by dividing the imidization index A by the imidization index B is calculated as the imidization rate of the resin. In measuring the imidization rate, the resin to be measured for imidization rate can be obtained from the composition by, for example, the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water and crystallized to precipitate the resin, which is then filtered. The filtrate is collected, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and crystallized, filtered, and dried at 40°C for 20 hours to obtain the resin.

[0075] [Weight-average molecular weight] The weight-average molecular weight of the first specific resin is preferably 2,500 or more, more preferably 4,000 or more, even more preferably 8,000 or more, particularly preferably 12,000 or more, even more preferably 16,000 or more, and most preferably 20,000 or more. The upper limit of the above weight-average molecular weight is not particularly limited, but for example it is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 70,000 or less, and particularly preferably 50,000 or less. The number-average molecular weight of the first specific resin is preferably 1,500 or more, more preferably 3,000 or more, even more preferably 6,000 or more, and even more preferably 10,000 or more. The upper limit of the above number-average molecular weight is not particularly limited, but for example it is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. The degree of dispersion of the first specific resin, expressed as weight-average molecular weight / number-average molecular weight, is preferably 5.0 or less, more preferably 4.5 or less, and even more preferably 4.0 or less. The above degree of dispersion is not particularly limited, but is preferably 1.5 or more.

[0076] [Method for producing the first specific resin] The first specific resin may be produced, for example, by the method described in paragraphs 0134-0136 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference. Alternatively, it may be synthesized by other known methods.

[0077] [Content] The content of the first specific resin in the photosensitive resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the photosensitive resin composition. Furthermore, the content of the resin in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the photosensitive resin composition. The photosensitive resin composition of the present invention may contain only one type of the first specific resin, or it may contain two or more types. When two or more types are included, it is preferable that the total amount is within the above range.

[0078] The photosensitive resin composition of the present invention may also preferably contain at least two types of resins. Specifically, the photosensitive resin composition of the present invention may contain a total of two or more types of the first specific resin and other resins described later, or it may contain two or more types of the first specific resin, but it is preferable that it contains two or more types of the first specific resin. When the photosensitive resin composition of the present invention contains two or more types of the first specific resin, it is preferable, for example, to contain two or more polyimide precursors that have different structures derived from dianhydrides.

[0079] <Second Specific Resin> The second photosensitive resin composition is at least one resin selected from the group consisting of polyimide precursors and polyimides, and includes a resin containing at least one of the repeating units represented by formula (1-1) and the repeating units represented by formula (2-1), and all X in the following formula (1-1) contained in the above resin １ and X in equation (2-1) ２ For all of X １ or X ２ The proportion of structures whose structure is represented by the following formula (X-1) is between 10 and 40 mol%, and X １ or X ２ The proportion of the structure represented by the following formula (X-2) is 60 to 90 mol%, and all of the Y in formula (1-1) contained in the resin is １and Y in equation (2-1) ２ Y for all of １ or Y ２ If the proportion of structures represented by formula (Y-2) is 80-100 mol%, and includes repeating units represented by formula (1-1), then R is included in all repeating units represented by formula (1-1). １ and R ２ R for all of １ or R ２ The composition contains a resin (second specific resin) in which the proportion of a structure represented by formula (R-1) is 50 to 90 mol%. The second photosensitive resin composition preferably contains a polyimide precursor as the second specific resin.

[0080] A preferred embodiment of formulas (1-1) and (2-1) in the second specific resin is that X in all of the formulas (1-1) included １ and X in equation (2-1) ２ For all of X １ or X ２ The proportion of structures whose structure is represented by equation (X-1), X １ or X ２ The proportion of structures represented by equation (X-2), and Y in all of the included equations (1-1). １ and Y in equation (2-1) ２ Y for all of １ or Y ２ The proportion of structures represented by equation (Y-2), and the R contained in all repeating units represented by equation (1-1) when it includes the repeating unit represented by equation (1-1). １ and R ２ R for all of １ or R ２ Except for the fact that the proportion of structures represented by formula (R-1) is limited as described above, this is the same as the preferred embodiment of formulas (1-1) and (2-1) in the first specific resin.

[0081] In the second specific resin, X in formula (1-1) １ and X in equation (2-1) ２ For all of X １ or X ２The proportion of materials having the structure represented by formula (X-1) is preferably 15 to 35 mol%, and more preferably 20 to 30 mol%.

[0082] In the second specific resin, X in formula (1-1) １ and X in equation (2-1) ２ For all of X １ or X ２ The proportion of the structure represented by formula (X-2) is preferably 65 to 85 mol%, and more preferably 70 to 80 mol%.

[0083] In the second specific resin, X in formula (1-1) １ and X in equation (2-1) ２ For all of X １ or X ２ The sum of the proportion of materials with the structure represented by formula (X-1) and the proportion of materials with the structure represented by formula (X-2) is preferably 75 mol% or more, more preferably 85 mol% or more, and even more preferably 95 mol% or more. Furthermore, a sum of 99 mol% or more is also a preferred embodiment. The upper limit of the above sum is not particularly limited and may be 100 mol%.

[0084] In the second specific resin, Y in all of formulas (1-1) １ and Y in equation (2-1) ２ Y for all of １ or Y ２ The proportion of the structure represented by formula (Y-2) is preferably 85 to 100 mol%, more preferably 90 to 100 mol%, and even more preferably 95 to 100 mol%.

[0085] If the second specific resin contains repeating units represented by formula (1-1), then R is included in all repeating units represented by formula (1-1). １ and R ２ R for all of １ or R ２ The proportion of the structure represented by formula (R-1) is preferably 60 to 85 mol%, and more preferably 65 to 80 mol%.

[0086] The content of repeating units represented by formula (1-1) and formula (2-1) relative to all repeating units in the second specific resin is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. A content of 99 mol% or more is also a preferred embodiment. The upper limit of the above content is not particularly limited, and it may be 100 mol% or less.

[0087] Furthermore, preferred embodiments of the repeating unit content in the second specific resin are the same as preferred embodiments of the repeating unit content in the first specific resin described above.

[0088] The preferred embodiments of the imidization rate, fluorine atom content, weight-average molecular weight, method for producing the specified resin, and content of the resin itself in the second specified resin are the same as those preferred embodiments in the first specified resin described above.

[0089] <Other Resins> The photosensitive resin composition of the present invention may contain the specified resin described above and other resins different from the specified resin (hereinafter also simply referred to as "other resins"). Examples of other resins include polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, etc. For example, by further adding (meth)acrylic resin, a photosensitive resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained. For example, in place of the polymerizable compound described later, or in addition to the polymerizable compound described later, a polymerizable compound with a high polymerizability value and a weight-average molecular weight of 20,000 or less (for example, the molar amount of polymerizable groups per 1 g of resin is 1 × 10) may be used. －３ By adding (meth)acrylic resin (in a quantity of mol / g or more) to a photosensitive resin composition, the coatability of the photosensitive resin composition, the solvent resistance of the pattern (cured product), and other properties can be improved.

[0090] If the photosensitive resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the photosensitive resin composition. If the photosensitive resin composition of the present invention contains other resins, the content of the other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the photosensitive resin composition. As a preferred embodiment of the photosensitive resin composition of the present invention, the content of other resins can also be low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the photosensitive resin composition. The lower limit of the above content is not particularly limited, and it is sufficient if it is 0% by mass or more. The photosensitive resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more resins, it is preferable that the total amount is within the above range.

[0091] <Polymerizable Compounds> The photosensitive resin composition of the present invention preferably contains polymerizable compounds. Examples of polymerizable compounds include radical crosslinking agents or other crosslinking agents.

[0092] [Radical Crosslinking Agent] The photosensitive resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0093] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 is even more preferred. From the viewpoint of the film strength of the resulting pattern (cured product), the photosensitive resin composition of the present invention may also preferably contain a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0094] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0095] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference. Furthermore, using the compounds described as E-1 to E-7 in the examples described later is also one of the preferred embodiments of the present invention.

[0096] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0097] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0098] Preferred radical crosslinking agents include 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.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0099] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0100] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0101] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0102] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0103] As radical crosslinking agents, radical crosslinking agents having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") are also preferred. Examples of crosslinking agent U include compounds described in paragraphs 0133 to 0143 of International Publication No. 2023 / 190064. This content is incorporated herein by reference.

[0104] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the photosensitive resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, and 1,6-methyl-1,5-pentanediol diacrylate. Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, and other difunctional acrylates and difunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200. From the viewpoint of suppressing warping of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the photosensitive resin composition of the present invention.Preferably used as monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds with a boiling point of 100°C or higher under normal pressure are also preferred as monofunctional radical crosslinking agents. Other examples of bifunctional or more functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0105] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the photosensitive resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0106] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0107] [Other Crosslinking Agents] The photosensitive resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon photosensitivity with a photoacid generator or photobase generator, and more preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator in the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0108] The photosensitive resin composition of the present invention contains a photosensitive agent. The photosensitive resin composition of the present invention preferably contains a photopolymerization initiator or a photoacid generator as the photosensitive agent, more preferably a photopolymerization initiator, and even more preferably a photoradical polymerization initiator.

[0109] [Photopolymerization Initiator] The photosensitive resin composition of the present invention preferably contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical polymerization initiator. There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0110] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0111] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0112] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0113] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0114] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0115] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0116] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0117] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0118] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, compounds described in International Publication No. 2013 / 167515, and others, the contents of which are incorporated herein by reference.

[0119] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In photosensitive resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0120]

[0121] Among these, the photosensitive resin composition of the present invention preferably contains a ketoxime compound as a photoradical polymerization initiator or the like. The ketoxime compound preferably contains a compound represented by the following formula (PI-1). In formula (PI-1), R Ｐ１ represents a monovalent organic group, R Ｐ２ R represents an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aryl group, or alkylaminocarbonyl group. Ｐ３ This represents an aryl group.

[0122] In formula (PI-1), R Ｐ１ Preferably, R is an aryl group having 3 to 10 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, an aryloxycarbonylalkyl group having 4 to 20 carbon atoms, an arylthioalkyl group having 4 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an arylroyl group having 7 to 20 carbon atoms, an arylroyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms. Ｐ１ ~R Ｐ３ It may have further substituents.

[0123] In formula (PI-1), R Ｐ２ Preferably, the group is an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, an aryloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 3 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

[0124] In formula (PI-1), R Ｐ３ The group is preferably an aryl group having 3 to 20 carbon atoms, such as a phenyl group or a carbazole group.

[0125] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (SARTOMER Examples include those manufactured by ARKEMA. In addition, oxime compounds with the following structure, and the compounds described as B-1 to B-6 in the examples described later, can also be used.

[0126] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom may be used. Also, oxime compounds having a nitro group as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton may be used. These contents are incorporated herein by reference.

[0127] In addition, compounds described in paragraphs 0113 to 0117 of Japanese Patent Publication No. 2023-058585 may be used as photopolymerization initiators. This description is incorporated into the present specification.

[0128] Among these, the photosensitive resin composition is preferably made to contain a compound represented by any of the following formulas (B-1) to (B-3) as a photopolymerization initiator.

[0129] If the photosensitive resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the photosensitive resin composition. The composition may contain only one type of photopolymerization initiator or two or more types. If two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. In addition, since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0130] [Sensitizer] The photosensitive resin composition may contain a sensitizer. The sensitizer absorbs specific active radiation and enters an electronically excited state. When the sensitizer enters an electronically excited state, it comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. Suitable sensitizers include compounds such as benzophenone, Michlaz ketone, coumarin, pyrazole azo, anilino azo, triphenylmethane, anthraquinone, anthracene, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.Examples of sensitizers include Michla's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, and p-dimethylaminobenzylideneindanone. Non, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin Phosphorus, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, diethylaminobenzoate Examples include soamyl, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. Other sensitizing dyes may also be used. For details on sensitizing dyes, refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0131] When the photosensitive resin composition contains a sensitizer, the sensitizer content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive resin composition. The sensitizer may be used alone or in combination of two or more types.

[0132] [Chain Transfer Agent] The photosensitive resin composition of the present invention may contain a chain transfer agent. A chain transfer agent is defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２ Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0133] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0134] If the photosensitive resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the photosensitive resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0135] Furthermore, a preferred embodiment of the present invention is that the photosensitive resin composition of the present invention contains two or more polymerization initiators as polymerization initiators. Specifically, it is preferable that the photosensitive resin composition of the present invention contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and photoacid generator.

[0136] By including a photopolymerization initiator and a thermal polymerization initiator described later, pattern formation by exposure becomes possible, and radical polymerization also proceeds more easily during curing by the heating process described later, which may improve performance such as chemical resistance. When including a photopolymerization initiator and a thermal polymerization initiator described later, the content ratio of the thermal polymerization initiator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0137] The inclusion of a photoradical polymerization initiator and a photoacid generator may improve performance such as resolution. When a photopolymerization initiator and a photoacid generator are included, the content ratio of the photoacid generator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the photoacid generator.

[0138] [Thermal Polymerization Initiators] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals using thermal energy, thereby initiating or promoting the polymerization reaction of polymerizable compounds. By adding thermal radical polymerization initiators, the polymerization reaction of resins and polymerizable compounds can be advanced, thereby further improving solvent resistance.

[0139] Specifically, examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Publication No. 2008-063554, the contents of which are incorporated herein by reference. Examples of thermal polymerization initiators include azo initiators such as V-30, V-40, V-59, V601, V65, V-70, VF-096, VE-073, Vam-110, Vam-111 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), OTazo-15, OTazo-30, AIBN, AMBN, ADVN, ACVA (all manufactured by Otsuka Chemical Co., Ltd.); Pertetra A, Perhexa HC, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Perbutyl H, Permil H, Permil P, Permenta H, Per Octa H, Perbutyl C, Perbutyl D, Perhexyl D, Perloyl IB, Perloyl 355, Perloyl L, Perloyl SA, Naiper BW, Naiper BMT-K40 / M, Perloyl IPP, Perloyl NPP, Perloyl TCP, Perloyl OPP, Perloyl SBP, Permil ND, Perocta ND, Perhexyl ND, Perbutyl ND, Perbutyl NHP, Perhexyl PV, Perbutyl P, Perbutyl PV, Perhexa 250, Perocta O, Perhexyl O, Perbutyl O, Perbutyl L, Perbutyl 355, Perhexyl I, Perbutyl I, Perbutyl E, Perhexa 25Z, Perbutyl A, Perhexyl Z, Perbutyl ZT, Perbutyl Z (all manufactured by NOF Corporation), Kayaketal AM-C55, Trigonox 36-C75, Laurox, Percadox L-W75, Percadox CH-50L, Trigonox TMBH, Kayakumen H, Kayabutyl H-70, Percadox BC-FF, Kayahexa AD, Percadox 14, Kayabutyl C, Kayabutyl D, Kayahexa YD-E 85, Parkadox 12-XL25, Parkadox 12-EB20, Trigonox 22-N70, Trigonox 22-70E, Trigonox D-T50, Trigonox 423-C70, Kaya Ester CND-C70, Kaya Ester CND-W50, Trigonox 23-C70, Trigonox 23-W50N, Trigonox 257-C70, Kaya Ester P-70, Kaya Ester TMPO-70, Trigonox 121, Kaya Ester O, Kaya Ester HTP-65W, Kaya Ester AN,Trigonox 42, Trigonox F-C50, Kayabutyl B, Kayacarbon EH-C70, Kayacarbon EH-W60, Kayacarbon I-20, Kayacarbon BIC-75, Trigonox 117, Kayalen 6-70 (all manufactured by Kayaku Akzo Co., Ltd.), Luperox 610, Luperox 188, Luperox 844, Luperox 259, Luperox 10, Luperox 701, Luperox 11, Luperox 26, Luperox 80, Luperox 7, Luperox 270, Luperox P, Luperox Examples include Luperox 546, Luperox 554, Luperox 575, Luperox TANPO, Luperox 555, Luperox 570, Luperox TAP, Luperox TBIC, Luperox TBEC, Luperox JW, Luperox TAIC, Luperox TAEC, Luperox DC, Luperox 101, Luperox F, Luperox DI, Luperox 130, Luperox 220, Luperox 230, Luperox 233, and Luperox 531 (all manufactured by Arkema Yoshitomi Co., Ltd.).

[0140] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, based on the total solid content of the photosensitive resin composition. The photosensitive resin composition may contain only one type of thermal polymerization initiator or two or more types. If two or more types of thermal polymerization initiators are included, the total amount is preferably within the above range.

[0141] <Base Generator> The photosensitive resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the photosensitive resin composition contains a polyimide precursor, it is preferable that the photosensitive resin composition contains a base generator. By containing a thermal base generator in the photosensitive resin composition, for example, heating can promote the cyclization reaction of the precursor, resulting in good mechanical properties and chemical resistance of the cured product, and thus good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Known base-generating agents include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include the compounds described in paragraphs 0249-0275 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0142] Examples of base-generating agents include, but are not limited to, the following compounds. Furthermore, using the compounds described as I-1 to I-3 in the examples described later is also one of the preferred embodiments of the present invention.

[0143]

[0144] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0145] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0146] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0147] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0148] Furthermore, as a base-generating agent, it is preferable that the amino group is protected by a t-butoxycarbonyl group, from the viewpoint of storage stability and base generation by deprotection during curing.

[0149] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanol Luamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) Examples include, but are not limited to, ethers, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or its derivative is protected by a t-butoxycarbonyl group.

[0150] When the photosensitive resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the photosensitive resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0151] <Solvent> The photosensitive resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0152] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-A Suitable examples include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0153] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0154] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0155] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0156] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0157] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0158] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0159] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0160] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0161] In the present invention, one solvent selected from 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, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the photosensitive resin composition, an embodiment containing γ-valerolactone as the solvent is also a preferred embodiment of the present invention. In such embodiments, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content may be determined by considering the solubility of specific resins and other components contained in the photosensitive resin composition.Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide relative to the total mass of the solvent, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0162] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range. The boiling point of the solvent is preferably 80°C to 300°C. Specific examples of solvent boiling points include 150°C, 190°C, and 200°C. The upper limit of the solvent's explosion is preferably 5 vol% to 50 vol%. The lower limit of the solvent's explosion is preferably 0.5 vol% to 15 vol%.

[0163] <Metal Adhesion Modifying Agent> The photosensitive resin composition of the present invention preferably contains a metal adhesion modifying agent from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion modifying agents include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0164] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Application Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Application Publication No. 2011-128358. The following compounds are also preferable as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. R below represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.). Furthermore, using the compounds described as H-1 to H-4 in the examples described later is also one of the preferred embodiments of the present invention.

[0165]

[0166] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1). In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the multiple repeating units represented by formula (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercially available products can be used as such oligomer-type compounds, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0167] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0168] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0169] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total value is within the above range.

[0170] <Migration Inhibitor> The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the photosensitive resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0171] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0172] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0173] As other migration inhibitors, rust inhibitors described in paragraph 0094 of JP-A No. 2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A No. 2009-283711, compounds described in paragraph 0052 of JP-A No. 2011-059656, compounds described in paragraphs 0114, 0116 and 0118 of JP-A No. 2012-194520, compounds described in paragraph 0166 of WO 2015 / 199219, etc. can be used, and this content is incorporated herein.

[0174] Specific examples of the migration inhibitor include the following compounds.

[0175]

[0176] When the photosensitive resin composition of the present invention has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass based on the total solid content of the photosensitive resin composition.

[0177] The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, the total thereof is preferably within the above range.

[0178] <Polymerization inhibitor> The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic ring compounds, metal compounds, etc.

[0179] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-N,N-dioxide, and the like. This information is incorporated herein by reference. Furthermore, using the compounds described as J-1 to J-4 in the examples described later is also one of the preferred embodiments of the present invention.

[0180] If the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the photosensitive resin composition.

[0181] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0182] <Light Absorbers> The photosensitive resin composition of the present invention may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are incorporated herein by reference.

[0183] Furthermore, the photosensitive resin composition of the present invention may also preferably contain a photochromic compound. The photochromic compound is not particularly limited, but it is preferably a compound represented by any of the following formulas (A-b-1) to (A-b-6). In formula (Ab-1), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, R ４R is a hydrogen atom or any organic group, ５ R is a hydrogen atom or any organic group, ４ and R ５ They may bond to form a ring structure, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, Z １ -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, the dashed line represents a single bond or a double bond, and if the dashed line represents a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A-b-2) or equation (A-b-3), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ ha = C(R Ｚ ) - or = N -, R Ｚ L is a hydrogen atom or any organic group. ２ is any divalent linking group which may have substituents, and Z １ is -O, -S, or -NR ６ And, if the dashed line indicates a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A - b - 4), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ ha = C(R Ｚ ) - or = N -, R Ｚ L is a hydrogen atom or any organic group. ２ is any divalent linking group which may have substituents, and Z ２ =O, =S, or =NR ７ And R ７ is a hydrogen atom or any organic group, and the dashed part is a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A-b-5) or equation (A-b-6), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ ha = C(R Ｚ ) - or = N -, R Ｚ L is a hydrogen atom or any organic group. ２ is any divalent linking group which may have substituents, and Z ４ is -OH, -SH, -N(R ６ ) is one of H, and R ６ is a hydrogen atom or any organic group, An is a counter anion, and the dashed part is a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist.

[0184] In formula (Ab-1), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and it is preferable that each is any organic group. ２Examples of the above-mentioned arbitrary organic groups include hydrocarbon groups, alkoxy groups, allyloxy groups, etc. In formula (A-b-1), R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and is preferably a hydrogen atom. ３ Examples of the above-mentioned arbitrary organic groups include hydrocarbon groups, alkoxy groups, allyloxy groups, etc. Also, in formula (A-b-1), R ２ It is preferable that they bond to each other to form an alicyclic or aromatic ring, and more preferably that they form an aromatic ring. Examples of aromatic rings include fused polycyclic hydrocarbon rings such as benzene rings or naphthalene rings. The above alicyclic or aromatic ring may have further substituents insofar as the effects of the present invention are obtained. In formula (A-b-1), R ４ is a hydrogen atom or any organic group, and preferably any organic group. A hydrocarbon group is preferred as the organic group, and an alkyl group is more preferred. In formula (A-b-1), Z １ -O- is preferred. In formula (A-b-1), R ５ R is a hydrogen atom or any organic group, and preferably any organic group. A hydrocarbon group is preferred as the organic group. In formula (A-b-1), R ４ and R ５ It is preferable that they bond to form a ring structure. The formed ring structure is Z １ It is preferable that the ring structure is a five-membered or six-membered ring containing a heteroatom, and more preferably a six-membered ring. Furthermore, it is preferable that the above ring structure is an unsaturated aliphatic. Furthermore, the above ring structure may be further condensed with other ring structures. Other ring structures include aromatic hydrocarbon ring structures which may have substituents, and benzene ring structures or naphthalene ring structures which may have substituents are preferred. Examples of substituents include halogen atoms, nitro groups, alkoxy groups, etc. Among these, R ４ and R ５ The ring structure formed by the bonding is preferably a pyran ring structure which may be fused with the other ring structures mentioned above. ４ and R ５Examples of ring structures formed by the bonding of Z are shown below, but the present invention is not limited to these. In the structures below, Z １ Z in equation (A - b - 1) １ It is synonymous with L １ The # represents the connection point with X.

[0185] In formula (A-b-1), L １ is any divalent linking group which may have substituents, and is preferably an alkylene group, -C(CH ３ ) ２ - is more preferable. In formula (A-b-1), X is -NR ６ - is preferable. R ６ It is preferable that is an alkyl group which may have substituents. Examples of substituents include a hydroxyl group. ６ The preferred embodiment is the same for this as well. Also, in formula (A-b-1), X and L １ The ring structure containing is preferably a five-membered ring or a six-membered ring, and more preferably a five-membered ring.

[0186] In formula (Ab-2), R ２ , R ３ , L １ A preferred embodiment of X is R in formula (A-b-1). ２ , R ３ , L １ , similar to the preferred embodiment of X. In formula (A-b-2), L ２ It is preferably a hydrocarbon group which may have substituents, and more preferably an aromatic hydrocarbon group which may have substituents. Examples of substituents include alkoxy groups, nitro groups, halogen atoms, etc. ２ A specific example of a preferred embodiment is shown below. In the structure below, * represents Z in equation (A-b-2). ３ The connection point is, # is Z １ These represent the bonding sites, respectively. Note that geometric isomerism is not particularly limited in the following structure. In formula (A-b-2), Z １ It is preferable that it is -O.

[0187] In formula (A-b-2), Z ３ ha = C(R Ｚ ) - or = N - and = C(R Ｚ ) - Preferably R Ｚ R is a hydrogen atom or any organic group, and is preferably a hydrogen atom. ｚ When it is any organic group, examples include hydrocarbon groups, and alkyl groups are preferred.

[0188] In formula (Ab-3), R ２ , R ３ , L １ A preferred embodiment of X is R in formula (A-b-1). ２ , R ３ , L １ , similar to the preferred embodiment of X. In formula (A-b-3), L ２ and Z ３ A preferred embodiment is L in formula (A-b-2) ２ and Z ３ This is similar to the preferred embodiment. In formula (A-b-3), Z １ It is preferable that it is -O.

[0189] In formula (Ab-4), R ２ , R ３ , L １ A preferred embodiment of X is R in formula (A-b-1). ２ , R ３ , L １ , similar to the preferred embodiment of X. In formula (A-b-4), Z ３ A preferred embodiment is Z in formula (A-b-2) ３ This is similar to the preferred embodiment. In formula (A-b-4), L ２ It is preferably a hydrocarbon group which may have substituents, and more preferably a hydrocarbon ring group which may have substituents. Examples of substituents include alkoxy groups, nitro groups, halogen atoms, etc. ２ Specific examples of preferred embodiments are shown below. In the structure below, * represents Z ３ The connection point is, # is Z ２ These represent the connection points between the two elements. In formula (A-b-4), Z ２ It is preferable that = O.

[0190] In formula (A-b-5) or formula (A-b-6), R ２ , R ３ , L １ , X, Z ３ , L ２ A preferred embodiment is R in formula (A-b-2) or formula (A-b-3). ２ , R ３ , L １ X, Z ３ , L ２ This is similar to the preferred embodiment. In formula (A-b-5) or formula (A-b-6), Z ４ -OH is preferred. An is a counter anion, and its structure is not particularly limited and may be other components in the composition. For example, one example is a configuration in which the terminal carboxyl group of a particular resin becomes a counter anion.

[0191] The compound represented by formula (A-b-1) is preferably a compound having a maximum absorption wavelength at a wavelength of 340 to 380 nm. The compound represented by any of formulas (A-b-2) to (A-b-6) is preferably a compound having a maximum absorption wavelength at a wavelength of 400 to 700 nm. The compound represented by formula (A-b-1) is preferably a compound whose structure changes to that of any of formulas (A-b-2) to (A-b-6) upon irradiation with light of any wavelength between 340 and 380 nm. The compound represented by any of formulas (A-b-2) to (A-b-6) is preferably a compound whose structure changes to that of the compound represented by formula (A-b-1) upon irradiation with light of any wavelength between 400 and 700 nm, shielding from light, or heating. When a photosensitive resin composition contains a compound represented by any of formulas (A-b-2) to (A-b-6), it is possible to generate a compound represented by formula (A-b-1) by irradiating the composition or a film made from the composition with light of any wavelength between 400 and 700 nm, shielding it from light, or heating it. In this embodiment, if the compound represented by formula (A-b-1) has a maximum absorption wavelength between 340 and 380 nm, the focus margin is considered to be large.

[0192] Examples of photochromic compounds include, but are not limited to, the following compounds.

[0193] The content of the light absorber relative to the total solid content of the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass.

[0194] <Other Additives> The photosensitive resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding U.S. Patent Application Publication No. 2013 / 0034812), paragraphs 0101-0104, 0107-0109 of Japanese Patent Application Publication No. 2008-250074, and the contents of these are incorporated herein. When these additives are incorporated, it is preferable that their total content be 3% by mass or less of the solid content of the photosensitive resin composition of the present invention.

[0195] [Surfactants] Various surfactants can be used as surfactants, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0196] By incorporating a surfactant into the photosensitive resin composition of the present invention, the liquid properties (especially the fluidity) of the prepared coating liquid composition are further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further enhanced. Specifically, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid decreases, improving wettability to the surface to be coated and improving coatability to the surface to be coated. Therefore, it is possible to more favorably form a uniform film with less thickness variation.

[0197] Examples of fluorinated surfactants include the compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which are incorporated herein by reference. Fluorinated polymer compounds can also be preferably used as fluorinated surfactants, which include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Examples include the following compounds.

[0198] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As a fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0199] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0200] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0201] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0202] [Inorganic Particles] Examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0203] The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter of the inorganic particles is the primary particle diameter and also the volume-average particle diameter. The volume-average particle diameter can be measured, for example, by dynamic light scattering using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission, X-ray transmission, or laser diffraction / scattering.

[0204] [Organotitanium Compounds] By including organotitanium compounds in the photosensitive resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0205] Suitable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for photosensitive resin compositions and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), titanium diisopropoxidebis(ethylacetoacetate), etc. II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compound: for example, titanium tetraacetylacetonate and the like. VII) Titanate coupling agent: for example, isopropyltridodecylbenzenesulfonyl titanate and the like.

[0206] Among them, from the viewpoint of better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of the above I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound. Particularly, titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

[0207] It is also preferable to include a compound represented by the following formula (T-1) as the organotitanium compound or in place of the organotitanium compound. In formula (T-1), M is titanium, zirconium or hafnium, l1 is an integer of 0 to 2, l2 is 0 or 1, l1 + l2×2 is an integer of 0 to 2, m is an integer of 0 to 4, n is an integer of 0 to 2, and l1 + l2 + m + n×2 = 4, and R １１ are each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, and R １２ is a substituted or unsubstituted hydrocarbon group, and R ２ are each independently a group containing a structure represented by the following formula (T-2), and R ３ are each independently a group containing a structure represented by the following formula (T-2), and X Ａ are each independently an oxygen atom or a sulfur atom. In formula (T-2), X １ ~X ３ each independently represents -C(-*)= or -N=, * represents the bonding site with other structures, and # represents the bonding site with the metal atom.

[0208] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (T-1), m is preferably 2 or 4, and more preferably 2. In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1. Here, in formula (T-1), it is also preferable that l1 and l2 are 0 and m is 0, 2, or 4.

[0209] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R １１ A substituted or unsubstituted cyclopentadienyl ligand is preferred. Also, R １１ The cyclopentadienyl group, alkoxy group, and phenoxy group in the compound may be substituted, but an unsubstituted configuration is also a preferred embodiment of the present invention.

[0210] In formula (T-1), R １２ R is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. １２ The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. １２ The substituents in are preferably monovalent substituents, such as halogen atoms. １２ If is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. Among these, in formula (T-1), R １２ It is preferable that R is an unsubstituted phenylene group. １２ The phenylene group in this is preferably a 1,2-phenylene group.

[0211] In equation (T-1), m is 2 or greater, and R ２ If there are two or more of them, then the two or more R２ The structures of each may be the same or different. In equation (T-1), n ​​is 2 or greater, and R ３ If there are two or more of them, then the two or more R ３ The structures of each may be the same or different.

[0212] In formula (T-2), X １ ~X ３ Each of these independently represents -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[0213] Specific examples of compounds represented by formula (T-1) include, but are not limited to, the compounds corresponding to G-1 and G-2 in the examples.

[0214] When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0215] When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0216] [Antioxidant] The composition of the present invention may contain an antioxidant. By including an antioxidant as an additive, the elongation properties of the cured film and its adhesion to metal materials can be improved. Examples of antioxidants include phenol compounds, phosphite ester compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. A preferred phenol compound is a hindered phenol compound. Compounds having a substituent at the ortho position adjacent to the phenolic hydroxyl group are preferred. As the substituents mentioned above, substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms are preferred. Furthermore, compounds having both a phenol group and a phosphite ester group in the same molecule are also preferred as antioxidants. In addition, phosphorus-based antioxidants can also be suitably used as antioxidants. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosfepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-2-yl)oxy]ethyl]amine, and ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphate. Examples of commercially available antioxidants include ADEKA STUB AO-20, ADEKA STUB AO-30, ADEKA STUB AO-40, ADEKA STUB AO-50, ADEKA STUB AO-50F, ADEKA STUB AO-60, ADEKA STUB AO-60G, ADEKA STUB AO-80, and ADEKA STUB AO-330 (all manufactured by ADEKA Corporation). Furthermore, compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 may also be used as antioxidants, and this information is incorporated herein. Additionally, the compositions of the present invention may optionally contain latent antioxidants. Examples of latent antioxidants include compounds in which the antioxidant portion is protected by a protecting group, and which function as antioxidants when heated at 100 to 250°C or when heated at 80 to 200°C in the presence of an acid / base catalyst, thereby removing the protecting group.Examples of latent antioxidants include compounds described in International Publication No. 2014 / 021023, International Publication No. 2017 / 030005, and Japanese Patent Publication No. 2017-008219, the contents of which are incorporated herein by reference. Examples of commercially available latent antioxidants include ADEKA Arclus GPA-5001 (manufactured by ADEKA Corporation). Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol, and compounds represented by formula (3). Furthermore, using the compounds described as L-1 to L-3 in the examples described later is also one of the preferred embodiments of the present invention.

[0217] In formula (3), R ５ R represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), ６ R represents an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). ７ k represents a 1-4 valent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom, and a nitrogen atom. k represents an integer from 1 to 4.

[0218] The compound represented by formula (3) suppresses the oxidative degradation of aliphatic groups and phenolic hydroxyl groups in resins. Furthermore, it can suppress metal oxidation by providing rust prevention to metal materials.

[0219] Since it can act on both the resin and the metal material simultaneously, k is more preferably an integer between 2 and 4. Examples of R7 include alkyl groups, cycloalkyl groups, alkoxy groups, alkyl ether groups, alkylsilyl groups, alkoxysilyl groups, aryl groups, aryl ether groups, carboxyl groups, carbonyl groups, allyl groups, vinyl groups, heterocyclic groups, -O-, -NH-, -NHNH-, and combinations thereof, and may also have substituents. Among these, alkyl ether groups and -NH- are preferred from the viewpoint of solubility in the developer and metal adhesion, and -NH- is more preferred from the viewpoint of interaction with the resin and metal adhesion due to metal complex formation.

[0220] Examples of compounds represented by formula (3) include the following, but are not limited to the structures shown below.

[0221] The amount of antioxidant added is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the specific resin. Adding 0.05 parts by mass or more makes it easier to obtain effects that improve elongation characteristics and adhesion to metal materials even in high temperature and high humidity environments, while adding 10 parts by mass or less may improve the sensitivity of the resin composition to exposure. One type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount is within the above range.

[0222] Other additives include the compounds described in paragraphs 0249-0282 and 0316-0358 of International Publication No. 2022 / 145355. The foregoing description is incorporated herein by reference.

[0223] <Characteristics of the Photosensitive Resin Composition> The viscosity of the photosensitive resin composition of the present invention can be adjusted by the solid content concentration of the photosensitive resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２ If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0224] The flash point of the resin composition of the present invention is preferably 25°C to 150°C. Specific examples of flash points of the resin composition include 60°C, 90°C, and 100°C.

[0225] The number of particles with a diameter of 0.5 to 20 μm that may be contained in the resin composition of the present invention is preferably 100 or less, and more preferably 50 or less. There is no particular lower limit to the number of particles, and it may be 0. From a practical standpoint such as manufacturing costs, the number of particles is, for example, 0.1 or more, specifically 1 or more. Furthermore, the number of particles with a diameter of 0.1 to 0.5 μm that may be contained in the resin composition of the present invention is preferably 100 or less, and more preferably 50 or less. There is no particular lower limit to the number of particles, and it may be 0. From a practical standpoint such as manufacturing costs, the number of particles is, for example, 0.1 or more, specifically 1 or more.

[0226] In this invention, when the number of particles in the resin composition is small, the resulting cured film tends to have good tensile elongation properties. This is merely a hypothesis, but can be explained as follows: If particles are present in the cured film, the location of those particles is thought to act as a "trigger" for fracture. Therefore, by reducing the number of particles in the resin composition used to form the cured film, the "trigger" for fracture in the cured film can be reduced, and as a result, good tensile elongation properties can be obtained.

[0227] Furthermore, in this invention, a lower number of particles in the resin composition tends to improve the adhesion of the resulting cured film to various substrates. This is presumed to be because fewer particles reduce the "triggers for delamination."

[0228] <Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the stability of the resin composition over time is improved. Furthermore, the lower limit of the water content of the resin composition of the present invention is preferably 0.001% by mass or more, can be 0.05% by mass or more, and can be 0.5% by mass or more, from the viewpoint of reducing the effort required to manage storage conditions, imparting adhesion, and imparting developability. Specific examples of the water content of the composition of the present invention include, for example, 0.05% by mass, 0.2% by mass, and 1.4% by mass. Methods for maintaining the water content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.

[0229] From the viewpoint of insulation, reliability, etc., the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Furthermore, from the viewpoint of reducing the effort required to reduce the metal content, mechanical properties, adhesion, etc., the lower limit of the metal content in the resin composition of the present invention can be 0.001 ppm by mass or more, and can also be 0.01 ppm by mass or more. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, manganese, aluminum, titanium, cobalt, zinc, tin, etc., but excludes metals included as complexes of organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range. Specific examples of the metal content in the resin composition of the present invention include, for example, 0.002 ppm by mass, 0.05 ppm by mass, 0.3 ppm by mass, etc.

[0230] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition, performing filter filtration on the raw materials constituting the resin composition, and performing distillation under conditions where contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0231] In the resin composition of the present invention, the content of the following substances is preferably 1 ppm by mass or less, more preferably 0.1 ppm by mass or less, and preferably substantially absent (below the detection limit).

[0232] <Substances> NMP, benzene, toluene, xylene, formaldehyde, trichloroethylene, ethylene oxide, dichloromethane, trichloromethane, tetrachloromethane, 1,2-dichloroethane, vinylidene chloride, vinyl chloride, 1,4-dioxane, acrylonitrile, PCB (polychlorinated biphenyl), PFOA (perfluorooctanoic acid), PFAS

[0233] Furthermore, in the resin composition of the present invention, the content of compounds that serve as raw materials for polyimide resin and compounds that serve as raw materials for compounds having radical polymerizable groups (so-called residual monomers) is preferably 10 ppm by mass or less, more preferably 5 ppm by mass or less, and even more preferably 1 ppm by mass or less. The lower limit of the content may be 0 ppm by mass. Also, from the viewpoint of reducing the effort required to reduce residual monomers and improving adhesion, the lower limit of the residual monomer content in the resin composition can be 0.001 ppm by mass or more, or 0.01 ppm by mass or more. Specific examples of residual monomer content include, for example, 0.002 ppm by mass, 0.05 ppm by mass, 0.3 ppm by mass, etc. Examples of such residual monomers include 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 3,3'-dihydroxybenzidine, 2,2'-dimethylbenzidine, 4,4'-diaminodiphenyl ether, etc. Furthermore, if multiple residual monomers are present, it is preferable that the total amount of these residual monomers falls within the numerical range described above.

[0234] <Restrictions on the substances contained in the photosensitive resin composition> The water content of the photosensitive resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the photosensitive resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0235] From the viewpoint of insulating properties, the metal content of the photosensitive resin 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 even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0236] Furthermore, methods for reducing metal impurities unintentionally included in the photosensitive resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the photosensitive resin composition of the present invention, performing filter filtration on the raw materials constituting the photosensitive resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0237] When considering its use as a semiconductor material, the photosensitive resin composition of the present invention preferably contains less than 500 ppm by mass of halogen atoms, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of preventing wiring corrosion. In particular, the amount of halogen atoms present in the form of halogen ions is preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0238] Conventional containers can be used as containers for the photosensitive resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and the photosensitive resin composition of the present invention, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0239] <Cured product of photosensitive resin composition> A cured product of the photosensitive resin composition of the present invention can be obtained by curing the photosensitive resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition. The curing of the photosensitive resin composition is preferably done by heating, with a heating temperature of 120°C to 400°C being more preferably, 140°C to 380°C being even more preferably, and 170°C to 350°C being particularly preferred. The form of the cured product of the photosensitive resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By pattern processing of the photosensitive resin composition, the shape of the cured product can also be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate of the photosensitive resin composition of the present invention upon curing is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the photosensitive resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0240] <Characteristics of the Cured Product of the Photosensitive Resin Composition> The imidization reaction rate of the cured product of the photosensitive resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured product of the photosensitive resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured product of the photosensitive resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0241] <Preparation of Resin Composition> The photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0242] When preparing the resin composition of the present invention, it is preferable that containers, pipes, etc., be made of stainless steel. It is preferable that the containers, pipes, etc., are cleaned with a solvent and free of residue. Furthermore, it is preferable that the preparation of the resin composition of the present invention be carried out in a cleanroom of class 10 to 10000. Moreover, when handling the resin composition of the present invention, such as when preparing it, it is preferable to use gloves with excellent solvent resistance. Excellent solvent resistance means, for example, conforming to ISO 374-1.

[0243] [Storage and Transportation of the Present Invention] When storing and transporting the resin composition of the present invention, a temperature range of -25°C to 15°C is preferred, and if it falls outside this range, the storage period is preferably less than 48 hours.

[0244] To remove foreign matter such as dust and fine particles from the resin composition of the present invention, filtration using a filter is preferable. The filter may be described in paragraph

[0287] of International Publication No. 2023 / 190064, and these descriptions are incorporated herein by reference. The filtration of the resin composition of the present invention is preferably carried out in a cleanroom of class 10 to 10000.

[0245] For the purpose of removing foreign matter such as dust and fine particles from the photosensitive resin composition of the present invention, filtration using a filter is preferable. As a filter, for example, the filter described in paragraph 0287 of International Publication No. 2023 / 190064 can be used. This description is incorporated herein by reference.

[0246] (Method for Manufacturing Cured Products) The method for manufacturing cured products of the present invention preferably includes a film-forming step of applying a photosensitive resin composition onto a substrate to form a film. The method for manufacturing cured products more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern. The method for manufacturing cured products particularly preferably includes the film-forming step, the exposure step, the developing step, and at least one of a heating step of heating the pattern obtained in the developing step and a post-development exposure step of exposing the pattern obtained in the developing step. Furthermore, the method for manufacturing cured products may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0247] <Film Formation Process> The photosensitive resin composition of the present invention can be used in a film formation process in which it is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a film formation process in which the photosensitive resin composition is applied to a substrate to form a film.

[0248] [Substrate] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. These substrates may have layers such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) on their surface. The shape of the substrate is not particularly limited and may be circular or rectangular. If the substrate is circular, for example, a diameter of 100 to 450 mm is preferred, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the shorter side is preferred to be 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped, preferably panel-shaped, substrate (substrate) is used.

[0249] When a photosensitive resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0250] Coating is a preferred method for applying the photosensitive resin composition onto a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are preferred, and from the viewpoint of both uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the photosensitive resin composition and the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Furthermore, a method can be applied in which a coating film, which has been previously applied and formed on a temporary support using the above application method, is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. In addition, a step of removing excess film at the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may be employed in which various solvents are applied to the substrate before applying the photosensitive resin composition to the substrate to improve the wettability of the substrate, and then the photosensitive resin composition is applied.

[0251] <Drying Process> After the film formation process (layer formation process), the film may be subjected to a drying process to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying process for drying the film formed in the film formation process. The drying process is preferably performed after the film formation process and before the exposure process. The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0252] <Exposure Process> The above film may be subjected to an exposure process in which the film is selectively exposed. The method for manufacturing the cured product may include an exposure process in which the film formed by the film formation process is selectively exposed. Selective exposure means exposing a part of the film. By selective exposure, exposed areas (exposed parts) and unexposed areas (unexposed parts) are formed in the film. The amount of exposure is not particularly limited as long as the photosensitive resin composition of the present invention can be cured, but for example, it may be 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0253] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0254] In relation to the light source, the exposure wavelength can be found in: (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths: g, h, i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２Examples of exposure methods include (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For the photosensitive resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the film made of the photosensitive resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0255] <Post-exposure heating step> The above film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0256] <Development Process> The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a cured product of the present invention may include a development process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the film is removed by the development process is called negative development, and development in which the exposed part of the film is removed by the development process is called positive development.

[0257] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0258] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. For example, the basic compounds described in paragraph 0300 of International Publication No. 2023 / 190064 can be used, and TMAH is more preferred. The content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer. The description in paragraph 0300 of International Publication No. 2023 / 190064 is incorporated herein by reference.

[0259] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph 0387 of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0260] When the developer contains an organic solvent, one or more organic solvents can be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0261] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the above content may be 100% by mass.

[0262] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0263] [Method of supplying developer] There are no particular restrictions on the method of supplying the developer as long as a desired pattern can be formed. These include immersing a substrate on which a film has been formed in the developer, paddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, a method of supplying it with a spray nozzle is more preferred. In addition, a step may be adopted in which the developer is continuously supplied with a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is supplied again with a straight nozzle, and the substrate is spun to remove the developer from the substrate. This step may be repeated multiple times. Examples of methods of supplying the developer in the development process include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept in a nearly stationary state on the substrate, a step in which the developer is vibrated on the substrate with ultrasound, etc., and a step that combines these.

[0264] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0265] In the developing process, after processing with the developer, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer in contact with the pattern dries completely may be employed.

[0266] The resin composition of the present invention preferably does not solidify at a concentration of 0.5 to 99.5% by mass when mixed with a developer. Furthermore, it is preferable that the resin composition of the present invention can be separated into developer components and resin composition components by methods such as distillation after mixing with a developer.

[0267] [Rinsing Solution] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0268] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0269] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. The organic solvents are preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, and even more preferably cyclohexanone and PGMEA.

[0270] When the rinsing solution contains an organic solvent, the amount of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0271] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents. When the resin composition of the present invention is mixed with the rinse solution, it is preferable that it does not solidify at a concentration of 40 to 90% by mass.

[0272] [Method of supplying rinsing solution] There are no particular restrictions on the method of supplying the rinsing solution as long as a desired pattern can be formed. These include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinsing solution, the removal of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing solution with a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply with a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. That is, the rinsing process is preferably a process of supplying the rinsing solution to the film after exposure using a straight nozzle or continuously supplying it, and it is more preferable to supply the rinsing solution using a spray nozzle. Possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0273] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0274] <Heating Step> The pattern obtained by the developing step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the developing step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the developing step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a developing step, or a film obtained by a film formation step is heated. In the heating step, resins such as polyimide undergo cyclization to become resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C. Furthermore, in the heating process, the amount of volatilization of components with a boiling point of 150°C or higher is preferably 5000 ppm or less, and more preferably 500 ppm or less, relative to the gas flow rate in the heating process. The heating process can also be carried out, for example, by the method described in paragraphs 0326-0332 of International Publication No. 2023 / 190064. This description is incorporated into the present specification.

[0275] <Post-development exposure step> The pattern obtained in the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a post-development exposure step in which the pattern after the development step is exposed, either in place of the heating step or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, reactions such as the cyclization of polyimide precursors etc. by photosensitivity of a photobase generator, or the elimination of acid-degradable groups by photosensitivity of a photoacid generator can be promoted. In the post-development exposure step, it is sufficient for at least a part of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The amount of exposure in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. ２ Preferably, 100 to 15,000 mJ / cm² ２ This is more preferable. The post-development exposure step can be performed, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

[0276] <Metal Layer Formation Process> The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation process in which a metal layer is formed on the pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process).

[0277] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0278] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7888181B2, and U.S. Patent No. 9177926B2 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of the plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0279] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0280] <Applications> The manufacturing method of the cured product of the present invention, or the fields in which the cured product can be applied, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or etching to form patterns on insulating films for the above-mentioned mounting applications. For more information on these applications, please refer to, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimide Fundamentals and Applications," NTS, August 2010.

[0281] The method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used for manufacturing printing plates such as offset plates or screen printing plates, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0282] (Laminate and Method for Manufacturing a Laminate) The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate is a laminate containing two or more layers made of the cured product, and may be a laminate with three or more layers. Of the two or more layers made of the cured product included in the above laminate, at least one is made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product due to the above shrinkage, it is also preferable that all the layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0283] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[0284] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer preferably included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer formation step described above. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer formation step of forming a metal layer on a layer made of cured material, which is performed multiple times during the manufacturing process of the cured material. The preferred embodiment of the metal layer formation step is as described above. As the laminate, for example, a laminate is preferred that includes at least three layers in which a first layer made of cured material, a metal layer, and a second layer made of cured material are laminated in this order. It is preferable that both the first layer made of cured material and the second layer made of cured material are layers made of cured material of the present invention. The photosensitive resin composition of the present invention used to form the first layer made of cured material and the photosensitive resin composition of the present invention used to form the second layer made of cured material may be compositions with the same composition or compositions with different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0285] <Lamination Process> The method for manufacturing a laminate of the present invention preferably includes a lamination process. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. However, the method may also involve repeating at least one of the following: (a) film formation process and (d) heating process and post-development exposure process. Furthermore, at least one of the following: (d) heating process and post-development exposure process may be followed by (e) metal layer formation process. Needless to say, the lamination process may further include the above-mentioned drying process and the like as appropriate.

[0286] If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0287] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may have the same composition, shape, film thickness, etc., or they may be different.

[0288] In the present invention, it is particularly preferable to form a cured product (resin layer) of the photosensitive resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination step of stacking the photosensitive resin composition layer (resin layer) of the present invention and the metal layer formation step, the photosensitive resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0289] (Surface Activation Treatment Step) The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the photosensitive resin composition layer is surface activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment step may be performed on the photosensitive resin composition layer before the metal layer formation step. The surface activation treatment may be performed on at least a portion of the metal layer, or on at least a portion of the photosensitive resin composition layer after exposure, or on at least a portion of both the metal layer and the photosensitive resin composition layer after exposure. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and it is more preferable to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the photosensitive resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion with the photosensitive resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the photosensitive resin composition layer (resin layer) after exposure. Thus, by performing a surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion between the surface-activated layer and the metal layer or resin layer provided on the surface-activated layer can be improved. In particular, when the photosensitive resin composition layer is cured, such as when developing negative film, it is less susceptible to damage from the surface treatment and adhesion is easily improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0290] (Semiconductor Devices and Methods for Manufacturing the Same) The present invention also discloses semiconductor devices including a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the photosensitive resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0291] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0292] <Synthesis of Polyimide Precursors> [Synthesis Example P-1: Synthesis of Resin P-1] 15.0 g (48.4 mmol) of 4,4'-oxydiphthalic anhydride, 4.74 g (16.1 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride, 12.0 g (92.3 mmol) of 2-hydroxyethyl methacrylate, 4.67 g (39.5 mmol) of 2-isobutoxyethanol, 0.05 g of hydroquinone, 22.7 g of pyridine (287 mmol), and 75 g of diglyceride (diethylene glycol dimethyl ether) are mixed. The mixture is stirred at 60°C for 4 hours to produce a mixture of diesters of 4,4'-oxydiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic anhydride, 2-hydroxyethyl methacrylate, and 2-isobutoxyethanol. Next, the reaction mixture was cooled to -10°C, and while maintaining the temperature at -10±4°C, 16.14 g (134.1 mmol) of SOCl was added. ２After adding over 60 minutes, the reaction mixture is stirred at room temperature for 2 hours. Next, a solution of 12.06 g (56.8 mmol) of 4,4'-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at -5 to 0°C. Then, the reaction mixture is reacted at 15°C for 1 hour, after which 11.9 g of ethanol is added and the mixture is stirred at room temperature for 2 hours. After adding 0.05 g of hydroquinone, the reaction mixture is added dropwise to 2 liters of water over 1 hour while stirring at a rate of 400 rpm (revolutions per minute) to precipitate the polyimide precursor. The polyimide precursor is obtained by filtration, and the obtained polyimide precursor is dried under reduced pressure at 45°C for 1 day to obtain the crude polyimide precursor (P-1). The obtained crude is then dissolved in 270 g of tetrahydrofuran. The dissolution is added dropwise to 2 liters of water over 1 hour while stirring at a rate of 400 rpm (revolutions per minute) to precipitate the polyimide precursor. The polyimide precursor is obtained by filtration, and the obtained polyimide precursor is dried under reduced pressure at 45°C for 1 day to obtain polyimide precursor (P-1). The weight-average molecular weight of this polyimide precursor (P-1) is 23,000. １ ¹H-NMR confirmed that the obtained polyimide precursor (P-1) is presumed to contain repeating units represented by the following formula (P-1). １ ¹H-NMR confirmed that the imidization rate of the polyimide precursor was 0% and the HEMA introduction rate was 70%.

[0293] [Synthesis Examples P-2 to P-9, P-11 to P-19, CP-1 to CP-6: Synthesis of resins P-2 to P-9, P-11 to P-19, CP-1 to CP-6] Resins P-2 to P-9, P-11 to P-19 and CP-1 to CP-6 were synthesized in the same manner as in Synthesis Example P-1, except that the acid anhydride, diamine, and alcohol used in combination with HEMA as described in the remaining structure were changed to those listed in the table below. The imidization rate and side chain introduction rate are listed in the table.

[0294] [Synthesis Example P-10: Synthesis of Resin P-10] 15.3 g (49.2 mmol) of 4,4'-oxydiphthalic anhydride, 4.83 g (16.4 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride, 12.0 g (132 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 10.7 g of pyridine (135 mmol), and 60 g of gamma-butyrolactone are mixed. The mixture is stirred at 45°C for 6 hours to produce a mixture of diesters of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate of 3,3',4,4'-biphenyltetracarboxylic anhydride. Next, the reaction mixture is cooled to 0–5°C, and while maintaining the temperature at 0–5°C, a solution of 27.1 g (131 mmol) of N,N'-dicyclohexylcarbodiimide (DCC) dissolved in 21.3 g of gamma-butyrolactone is added dropwise over 60 minutes. Then, a solution of 12.40 g (58.4 mmol) of 4,4'-diaminodiphenyl ether dissolved in 75 g of NMP is added dropwise over 60 minutes. After the addition is complete, the mixture is stirred at room temperature for 2 hours, then 24.2 g of ethanol is added, and the mixture is stirred at room temperature for 1 hour. After the reaction is complete, the solution is diluted with 56.9 g of 2-propanol. After removing the solid components by vacuum filtration, the solution is added dropwise over 1 hour while stirring at 400 rpm to a mixture of 1480 g of 2-propanol and 512 g of the solution to precipitate the polyimide precursor. The polyimide precursor was obtained by filtration, and the obtained polyimide precursor was dried under reduced pressure at 45°C for 1 day to obtain the crude polyimide precursor (P-10). Next, the obtained crude was dissolved in 200 g of tetrahydrofuran. The solution was added dropwise to 2 liters of water over 1 hour while stirring at a rate of 400 rpm (revolutions per minute) to precipitate the polyimide precursor. The polyimide precursor was obtained by filtration, and the obtained polyimide precursor was dried under reduced pressure at 45°C for 1 day to obtain the polyimide precursor (P-10). The weight-average molecular weight of this polyimide precursor (P-10) is 21,000. ¹H-NMR confirmed that the obtained polyimide precursor (P-10) is presumed to contain repeating units represented by the following formula (P-10). １¹H-NMR confirmed that the imidation rate of the polyimide precursor was 15% and the HEMA introduction rate was 100%.

[0295] [Synthesis Example P-20, CP-7: Synthesis of Resins P-20 and CP-7] Resins P-20 and CP-7 were synthesized in the same manner as in Synthesis Example P-10, except that the acid anhydride and diamine used were changed to those listed in the table below. The imidization rate and side chain introduction rate are shown in the table.

[0296]

[0297] The details of the abbreviations in the table are as follows. In the table, the column for "HEMA introduction rate" indicates the proportion of HEMA among the side chain units listed below. The remainder is a structure derived from 2-Isobutoxyethanol.

[0298] <Examples and Comparative Examples> In each example, the components listed in the table below were mixed to obtain each photosensitive resin composition. Similarly, in each comparative example, the components listed in the table below were mixed to obtain each comparative composition. Specifically, the amount of each component listed in the table in the solid content was the amount (mass%) indicated in the "Composition (%)" column of the table. The amount of solvent used was the amount of solvent mixed at the ratio indicated in the "Solvent Ratio" column so that the solid content concentration in the composition was the value indicated in the "Solid Content Concentration [mass%]" column of the table. The obtained photosensitive resin compositions and comparative compositions were pressure filtered using a PTFE (polytetrafluoroethylene) filter with a pore width of 0.45 μm. In the table, "-" indicates that the composition does not contain the corresponding component.

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306] Details of each component listed in the table are as follows:

[0307] [Resins (Polyimide Precursors)] ・Resins P-1 to P-20, Resins CP-1 to CP-7: Synthetic products of the above

[0308] [Polymerization Initiators] ・B-1 to B-6: Compounds with the following structure

[0309] [Sensitizer] ・C-1: Compound with the following structure

[0310] [Light absorber] ・D-1: Compound with the following structure

[0311] [Polymerizable compounds] ・E-1 to E-7: Compounds with the following structures

[0312] [Migration Inhibitors] • F-1 to F-2: Compounds with the following structure • F-3: 8-azaadenine • F-4: 1H-tetrazole • F-5: Compound with the following structure

[0313] [Metal Complexes] • G-1 to G-2: Compounds with the following structures (iPr represents an isopropyl group, and Et represents an ethyl group).

[0314] [Silane coupling agent (metal adhesion modifier)] • H-1 to H-2, H-4: Compounds with the following structure • H-3: KBM-503 (Compound with the following structure, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0315] [Thermal base generating agent] ・I-1: Compound with the following structure ・I-2, I-3: Compound with the following structure

[0316] [Polymerization inhibitors] ・J-1 to J-4: Compounds with the following structure

[0317] [Surfactants] ・K-1: BYK-333 (manufactured by Bic Chemie Japan Co., Ltd.)

[0318] [Antioxidants] ・L-1: Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate ・L-2 to L-3: Compounds with the following structure

[0319] [Thermal polymerization initiator] ・M-1: Perbutyl P (manufactured by NOF Corporation)

[0320] [Solvents] GBL: γ-butyrolactone DMSO: dimethyl sulfoxide γ-valerolactone: γ-valerolactone NMP: N-methylpyrrolidone CP: cyclopentanone Ethyl lactate: ethyl lactate 3-methoxy-N,N-dimethylpropanamide: 3-methoxy-N,N-dimethylpropanamide NEP: N-ethylpyrrolidone

[0321] <Measurement and Evaluation> [Measurement of Transmittance] In each example or comparative example, if "SP" is written in the "Coating Method" column, the prepared photosensitive resin composition or comparative composition is applied to a 1 mm thick quartz substrate by spin coating. In the example where "SL" is written in the "Coating Method" column, the photosensitive resin composition is applied to the same quartz substrate by slit coating. The quartz substrate is dried on a hot plate at 100°C for 5 minutes to form a photosensitive resin composition layer of uniform thickness of 7.5 μm on the quartz substrate. The i-line transmittance of the photosensitive resin composition layer is measured using a spectrophotometer. The evaluation results are recorded in the "Transmittance (%)" column in the table below.

[0322] [Measurement of Film Dissolution Rate] In each example or comparative example, the prepared photosensitive resin composition or comparative composition is applied to a silicon wafer by spin coating (SP) or slit coating (SL). The method used is indicated in the "Coating Method" column of the table. The silicon wafer is dried on a hot plate at 100°C for 5 minutes to form a uniform photosensitive resin composition layer of 7.5 μm thickness on the silicon wafer. The time until the photosensitive resin composition layer disappears is measured using a developer (ACTES ADE-3000) with cyclopentanone as the developer, and this time is defined as BT (sec). The film dissolution rate is calculated using the following formula. The evaluation results are indicated in the "Film Dissolution Rate (μm / sec)" column of the table below. (Formula) Film thickness before exposure X (μm) / BT (sec) = Film dissolution rate (μm / sec)

[0323] [Measurement of C=C value] Tetramethylsilane is used as the reference substance, and the specific resin １ The molar amount of polymerizable groups in the resin is calculated from the ratio of the integrated intensity of the peak corresponding to each polymerizable group in the H-NMR chart to the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specified resin. The measurement results are recorded in the "C = C value (mol / g)" column in the table shown below.

[0324] [Measurement of Elongation (Elongation at Breaking)] In each example or comparative example, the prepared photosensitive resin composition or comparative composition is applied to a silicon wafer by spin coating (SP) or slit coating (SL) to form a photosensitive resin composition layer. The method used for application is indicated in the "Application Method" column of the table. The silicon wafer is dried on a hot plate at 100°C for 5 minutes to obtain a photosensitive resin composition layer with a uniform thickness of 12 μm after film formation on the silicon wafer. The obtained photosensitive resin composition layer is subjected to a test using an i-line stepper at a rate of 400 mJ / cm². ２Exposure is performed using a dumbbell-shaped mask with the specified exposure energy. The dumbbell shape is the No. 7 dumbbell shape described in JIS K 6251:2017. The photosensitive resin composition layer after exposure is developed with cyclopentanone for (7.5 μm / film dissolution rate) × 1.5 (sec), then rinsed with PGMEA (propylene glycol monomethyl ether acetate) to remove unexposed areas. Further heating is performed under a nitrogen atmosphere at a heating rate of 10°C / min, and a cured product is obtained by heating under the temperature and time conditions described in the "Film Forming Conditions" column of the table above. The cured resin layer is immersed in a 4.9 mass% hydrofluoric acid solution, and the dumbbell-shaped cured product (test piece) is peeled off from the silicon wafer (sample width 2 mm, sample length 35 mm). The obtained test specimens are subjected to a tensile testing machine (Instron model 5965) at a crosshead speed of 5 mm / min, under conditions of 25°C and 65% RH (relative humidity), and the elongation in the longitudinal direction of the specimen is measured in accordance with JIS-K7161-1 (2014). Each evaluation is performed six times, and the arithmetic mean of the elongation at the time of fracture is used as the index value. The evaluation results are recorded in the "Elongation (%)" column in the table below. Cases where test specimens could not be prepared due to low resistance to developing solution are recorded as "Insufficient developing resistance," and cases where test specimens could not be prepared due to low sensitivity to exposure are recorded as "Insufficient sensitivity."

[0325] [Measurement of Young's Modulus] The Young's modulus of the test specimens prepared using the elongation measurement method described above will be measured using a DMA850 (TA Instruments) at a crosshead speed of 5 mm / min, in an environment of 25°C and 65% RH (relative humidity), in accordance with JIS-K7161-1 (2014). The evaluation results will be recorded in the "Young's Modulus (GPa)" column in the table below.

[0326] [Resolution Evaluation] In each example or comparative example, the prepared photosensitive resin composition or comparative composition is applied to a silicon wafer by spin coating (SP) or slit coating (SL) to form a photosensitive resin composition layer. The method used is indicated in the "Coating Method" column of the table. The silicon wafer is dried on a hot plate at 100°C for 5 minutes to form a photosensitive resin composition layer of uniform thickness of 7.5 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer is exposed to light with a wavelength of 365 nm through a photomask (via shape) using a stepper. The exposure amount is set to the minimum diameter, the NA is set to 0.16, and the focus is set in the range of -10 to +10. The exposed photosensitive resin composition layer is developed with cyclopentanone for a time of (7.5 μm / film dissolution rate) × 1.5 [sec], and then rinsed with PGMEA (propylene glycol monomethyl ether acetate). The photosensitive resin composition layer after exposure is heated in a nitrogen atmosphere at a heating rate of 10°C / min, and a cured product is obtained by heating under the temperature and time conditions described in the "Film Forming Conditions" column of the table above. -Evaluation Criterion 1: Minimum Diameter- In the pattern obtained after curing, the diameter of the via pattern with the smallest aperture diameter among the via patterns in which the silicon wafer is exposed is defined as the "minimum diameter" and evaluated according to the evaluation criteria below. A smaller via diameter indicates better resolution and is a desirable result. The evaluation results are described in the "1" column of "Resolution" in the table below. A: Minimum diameter is 3 μm or less. B: Minimum diameter is greater than 3 μm and 4 μm or less. C: Minimum diameter is greater than 4 μm and 5 μm or less. -Evaluation Criterion 2: DOF- In the 5 μm via pattern obtained after curing, the bottom diameter is measured. The depth of field (DOF) is defined as the range in which the bottom diameter falls within ±5% of the mask diameter (4.75 μm ≤ bottom diameter ≤ 5.25 μm), and is evaluated according to the following evaluation criteria. A wider DOF is preferable because it reduces the impact of substrate warping and flatness during exposure. The evaluation results are recorded in column "2" of "Resolution" in the table below. A: DOF is 10 μm or more. B: DOF is 5 μm or more and less than 10 μm. C: DOF is less than 5 μm.

[0327] [Evaluation of TCT crack resistance] In each example or comparative example, the prepared photosensitive resin composition or comparative composition is applied to a silicon wafer on which Cu 10 μmL / S (line / space) wiring is formed by spin coating (SP) or slit coating (SL) to form a photosensitive resin composition layer. The method used for application is indicated in the "Application Method" column of the table. The silicon wafer is dried on a hot plate at 100°C for 5 minutes to obtain a photosensitive resin composition layer with a uniform thickness of 15 μm after film formation on the silicon wafer. The obtained photosensitive resin composition layer is subjected to exposure using a Ushio exposure machine (light source: 500 W / m²). 2 (Ultra-high pressure mercury lamp) 400 mJ / cm² 2 The entire silicon wafer is exposed with the exposure energy. The photosensitive resin composition layer after exposure is heated in a nitrogen atmosphere at a heating rate of 10°C / min, and a cured product is obtained by heating under the temperature and time conditions described in the "Film Forming Conditions" column of the table above. A TCT test (ES-57L manufactured by Hitachi Global Life Solutions, Ltd., repeating -55°C and 200°C for 1000 cycles) is performed on the obtained cured product, and the presence or absence of cracks at the interface between the Cu wiring and the cured product is observed using a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation), and evaluated according to the evaluation criteria below. The evaluation results are described in the "TCT Crack Resistance" column of the table below. -Evaluation Criteria- A: 0 cracks are found in 10 observation points. B: 1 crack is found in 10 observation points. C: 2 or more cracks are found in 10 observation points.

[0328]

[0329]

[0330] From the above results, it can be seen that the film formed from the photosensitive resin composition of the present invention has excellent resolution and excellent TCT crack resistance. The comparative compositions in Comparative Examples 1 to 7 have at least one of the following characteristics that does not conform to the specifications of the photosensitive resin composition of the present invention: transmittance, film dissolution rate, ethylenically unsaturated value, elongation at break, and Young's modulus. It can be seen that these comparative compositions have inferior resolution and are prone to cracking after the TCT described above.

Claims

1. A photosensitive resin composition comprising at least one resin selected from the group consisting of polyimide precursors and polyimides, and a photosensitive agent, satisfying the following (i) to (v): (i) A coating film with a thickness of 7.5 μm is formed, and the transmittance of the coating film at a wavelength of 365 nm is measured to be 20% or more. (ii) A coating film is formed, and the following film dissolution rate, calculated from the film thickness X of the coating film and the time BT until the coating film is completely dissolved by cyclopentanone, is 0.8 μm / sec or less: Film thickness X (μm) / BT (sec) = Film dissolution rate (μm / sec) (iii) The ethylenically unsaturated value of the resin is 2.3 mmol / g or less. (iv) The elongation at break of the cured product obtained by curing the photosensitive resin composition is 60% or more. (v) The Young's modulus of the cured product obtained by curing the photosensitive resin composition is 3.5 GPa or more.

2. The photosensitive resin composition according to claim 1, wherein the photosensitive agent comprises a photoradical polymerization initiator.

3. The photosensitive resin composition according to claim 2, comprising a ketoxime compound as the photoradical polymerization initiator.

4. The photosensitive resin composition according to claim 2, wherein the photoradical polymerization initiator comprises a compound represented by the following formula (PI-1). In formula (PI-1), R Ｐ１ represents a monovalent organic group, R Ｐ２ R represents an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aryl group, or alkylaminocarbonyl group. Ｐ３ This represents an aryl group.

5. The photosensitive resin composition according to claim 1, wherein the resin contains at least one of a repeating unit represented by the following formula (1-1) and a repeating unit represented by formula (2-1). In formula (1-1), A １ and A ２ each independently represents an oxygen atom or -NR ｚ -, R ｚ represents a hydrogen atom or a monovalent organic group, X １ represents an organic group having 4 or more carbon atoms, Y １ represents an organic group having 4 or more carbon atoms, R １ and R ２ each independently represents a hydrogen atom or a monovalent organic group. In formula (2-1), X ２ represents an organic group having 4 or more carbon atoms, Y ２ represents an organic group having 4 or more carbon atoms.

6. The photosensitive resin composition according to claim 5, wherein the resin comprises at least one of the following repeating unit 1-A and the following repeating unit 2-A. Repeating unit 1-A: A repeating unit represented by the formula (1-1), where X １ Repeating unit 2-A: A repeating unit represented by the following formula (X-1), where X ２ The repeating unit is represented by the following formula (X-1). In formula (X-1), each * independently represents a bonding site with a carbonyl group.

7. The photosensitive resin composition according to claim 6, wherein the total content of repeating unit 1-A and repeating unit 2-A relative to the total repeating units of the resin is 10 mol% or more.

8. The photosensitive resin composition according to claim 5, wherein the total content of the following repeating unit 1-A, repeating unit 2-A, repeating unit 1-B, repeating unit 2-B, repeating unit 1-C, and repeating unit 2-C in the resin is 99 mol% or more. Repeating unit 1-A: A repeating unit represented by the formula (1-1), where X １ Repeating unit 2-A: A repeating unit represented by the following formula (X-1), where X ２ Repeating unit 1-B: A repeating unit represented by the following formula (X-1), where X １ Repeating unit 2-B: A repeating unit represented by the following formula (X-2), where X ２ Repeating unit 1-C: A repeating unit represented by the following formula (X-2), where X １ Repeating unit 2-C: A repeating unit represented by the following formula (X-3), where X ２ The repeating unit is represented by the following formula (X-3). In formula (X-1), each * independently represents a bonding site with a carbonyl group. In formula (X-2), each * independently represents a bonding site with a carbonyl group. In formula (X-3), each * independently represents a bonding site with a carbonyl group.

9. The resin includes the repeating unit represented by formula (1-1), and all repeating units represented by formula (1-1) contain R １ and R ２ R for all of １ or R ２ The photosensitive resin composition according to any one of claims 5 to 8, wherein the proportion of a structure represented by the following formula (R-1) is 50 to 90 mol%. In equation (R-1), * represents A in equation (1-1). １ Or A ２ This represents the connection point.

10. The photosensitive resin composition according to any one of claims 5 to 8, wherein the resin comprises at least one of the following repeating unit 1-D and the following repeating unit 2-D. Repeating unit 1-D: A repeating unit represented by the formula (1-1), Y １ Repeating unit 2-D: A repeating unit represented by the following formula (Y-1) or formula (Y-2), Y ２ A repeating unit whose base is represented by the following formula (Y-1) or formula (Y-2). In formula (Y-1), each * independently represents a bonding site with a nitrogen atom. In formula (Y-2), each * independently represents a bonding site with a nitrogen atom.

11. The photosensitive resin composition according to claim 10, wherein the resin comprises at least one of the following repeating unit 1-E and the following repeating unit 2-E. Repeating unit 1-E: A repeating unit represented by the formula (1-1), Y １ Repeating unit 2-E: A repeating unit represented by formula (2-1), where Y ２ The repeating unit is represented by the formula (Y-2) above.

12. The photosensitive resin composition according to any one of claims 1 to 8, wherein the content of fluorine atoms in the resin is 0.01 mmol / g or less.

13. A photosensitive resin composition according to any one of claims 1 to 8, further comprising a photochromic compound.

14. The photosensitive resin composition according to claim 13, wherein the photochromic compound is a compound represented by any of the following formulas (A-b-1) to (A-b-6). In formula (Ab-1), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, R ４ R is a hydrogen atom or any organic group, ５ R is a hydrogen atom or any organic group, ４ and R ５ They may bond to form a ring structure, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, Z １ -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, the dashed line represents a single bond or a double bond, and if the dashed line represents a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A-b-2) or equation (A-b-3), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ ha = C(R Ｚ ) - or = N -, R Ｚ is a hydrogen atom or any organic group, L ２ is any divalent linking group which may have substituents, and Z １ is -O, -S, or -NR ６ And, if the dashed line indicates a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A - b - 4), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ ha = C(R Ｚ ) - or = N -, R Ｚ is a hydrogen atom or any organic group, L ２ is any divalent linking group which may have substituents, and Z ２ =O, =S, or =NR ７ And R ７ is a hydrogen atom or any organic group, and the dashed part is a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist. In equation (A-b-5) or equation (A-b-6), R ２ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ３ Each of these is independently a hydrogen atom, a halogen atom, or any organic group, and R ２ They may combine to form an alicyclic or aromatic ring, L １ X is any divalent linking group which may have substituents, and X is -O-, -S-, -NR ６ - is one of the following, R ６ is a hydrogen atom or any organic group, Z ３ ha = C(R Ｚ ) - or = N -, R Ｚ is a hydrogen atom or any organic group, L ２ is any divalent linking group which may have substituents, and Z ４ is -OH, -SH, -N(R ６ ) is one of H, and R ６ is a hydrogen atom or any organic group, An is a counter anion, and the dashed part is a double bond, or R ２ When two R atoms combine to form an aromatic ring, ３ It does not exist.

15. At least one resin selected from the group consisting of a polyimide precursor and a polyimide, the resin containing at least one of the repeating unit represented by the following formula (1-1) and the repeating unit represented by formula (2-1), and containing a photosensitizer, and for all of X in all of the following formulas (1-1) contained in the resin １ and X in formula (2-1) ２ for all of them, the proportion of X １ or X ２ being a structure represented by the following formula (X-1) is 10 to 40 mol%, and the proportion of X １ or X ２ being a structure represented by the following formula (X-2) is 60 to 90 mol%, and for all of Y in all of the following formulas (1-1) contained in the resin １ and Y in formula (2-1) ２ for all of them, the proportion of Y １ or Y ２ being a structure represented by the following formula (Y-2) is 80 to 100 mol%, and when containing the repeating unit represented by the formula (1-1), for all of R and R contained in all of the repeating units represented by the formula (1-1) １ and R ２ for all of them, the proportion of R １ or R ２ being a structure represented by the following formula (R-1) is 50 to 90 mol% of a photosensitive resin composition. In formula (1-1), A １ and A[[ID=第33]] ２ each independently represents an oxygen atom or -NR ｚ -, R ｚ represents a hydrogen atom or a monovalent organic group, X １ represents an organic group having 4 or more carbon atoms, Y １ represents an organic group having 4 or more carbon atoms, R １ and R ２ each independently represents a hydrogen atom or a monovalent organic group. In formula (2-1), X ２ represents an organic group having 4 or more carbon atoms, Y ２ [[ID=第50]]represents an organic group having 4 or more carbon atoms. In formula (X-1), * each independently represents a bonding site with a carbonyl group. In formula (X-2), * represents each independent site of attachment to a carbonyl group. In formula (Y-2), each * independently represents a bonding site with a nitrogen atom. In equation (R-1), * represents A in equation (1-1). １ Or A ２ This represents the connection point.

16. A photosensitive resin composition according to any one of claims 1 to 8 and 15, used for forming an interlayer insulating film for a redistribution layer.

17. A cured product obtained by curing a photosensitive resin composition according to any one of claims 1 to 8 and 15.

18. A laminate comprising two or more layers made of the cured product described in claim 17, wherein a metal layer is included between any of the layers made of the cured product.

19. A method for producing a cured product, comprising a film-forming step of applying a photosensitive resin composition according to any one of claims 1 to 8 and 15 onto a substrate to form a film.

20. A method for producing a cured product according to claim 19, comprising an exposure step of selectively exposing the above film and a developing step of developing the above film using a developer to form a pattern.

21. A method for producing a cured product according to claim 19, comprising a heating step of heating the above film to 50 to 450°C.

22. A method for manufacturing a laminate, comprising the method for manufacturing a cured product according to claim 19.

23. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product as described in claim 19.

24. A semiconductor device comprising the cured product described in claim 17.

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